Production of chemicals and fuels from biomass

ABSTRACT

Described are methods, reactor systems, and catalysts for converting biomass to fuels and chemicals in a batch and/or continuous process. The process generally involves the conversion of water insoluble components of biomass, such as hemicellulose, cellulose and lignin, to volatile C 2+ O 1-2  oxygenates, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, and mixtures thereof. In certain applications, the volatile C 2+ O 1-2  oxygenates can be collected and used as a final chemical product, or used in downstream processes to produce liquid fuels, chemicals and other products.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.61/489,135 filed on May 23, 2011.

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under an award providedby the U.S. Department of Energy, Award No. DE-EE0003044. The governmenthas certain rights in the invention.

TECHNICAL FIELD

The present invention is directed to catalysts and methods forconverting biomass into liquid fuels and chemicals.

BACKGROUND OF THE INVENTION

Increasing cost of fossil fuel and environmental concerns havestimulated worldwide interest in developing alternatives topetroleum-based fuels, chemicals, and other products. Biomass materialsare a possible renewable alternative to petroleum-based fuels andchemicals.

Lignocellulosic biomass includes three major components. Cellulose, aprimary sugar source for bioconversion processes, includes highmolecular weight polymers formed of tightly linked glucose monomers.Hemicellulose, a secondary sugar source, includes shorter polymersformed of various sugars. Lignin includes phenylpropanoic acid moietiespolymerized in a complex three dimensional structure. The resultingcomposition of lignocellulosic biomass is roughly 40-50% cellulose,20-25% hemicellulose, and 25-35% lignin, by weight percent.

Very few cost-effective processes exist for efficiently convertingcellulose, hemicellulose and lignin to components better suited forproducing fuels, chemicals, and other products. This is generallybecause each of lignin, cellulose and hemicellulose demands distinctprocessing conditions, such as temperature, pressure, catalysts,reaction time, etc., in order to effectively break apart their polymerstructure. Because of this distinctness, most processes are only able toconvert specific fractions of the biomass, such as cellulose andhemicellulose, leaving the remaining fractions behind for additionalprocessing or alternative uses.

Hot water extraction of hemicellulose from biomass, for example, hasbeen well documented. The sugars produced by hot water extraction arehowever unstable at high temperatures leading to undesirabledecomposition products. Therefore, the temperature of the water used forhot water extraction is limited, which can reduce the effectiveness ofthe hot water extraction.

Studies have also shown that it is possible to convert microcrystallinecellulose (MCC) to polyols using hot, compressed water and ahydrogenation catalyst (Fukuoka & Dhepe, 2006; Luo et al., 2007; and Yanet al., 2006). Typical hydrogenation catalysts include ruthenium orplatinum supported on carbon or aluminum oxide. However, these studiesalso show that only low levels of MCC are converted with thesecatalysts, and selectivity toward desired sugar alcohols is low.

APR and HDO are catalytic reforming processes that have recently shownto be promising technologies for generating hydrogen, oxygenates,hydrocarbons, fuels, and chemicals from oxygenated compounds derivedfrom a wide array of biomass. The oxygenated hydrocarbons includestarches, mono- and poly-saccharides, sugars, sugar alcohols, etc.Various APR methods and techniques are described in U.S. Pat. Nos.6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all to Cortright et al.,and entitled “Low-Temperature Hydrogen Production from OxygenatedHydrocarbons”); U.S. Pat. No. 6,953,873 (to Cortright et al., andentitled “Low-Temperature Hydrocarbon Production from OxygenatedHydrocarbons”); and U.S. Pat. Nos. 7,767,867; 7,989,664; and U.S. PatentPublication No. 2011/0306804 (to Cortright, and entitled “Methods andSystems for Generating Polyols”). Various APR and HDO methods andtechniques are described in U.S. Pat. Nos. 8,053,615; 8,017,818;7,977,517; and U.S. Patent Publication Nos. 2011/0257448; 2011/0245543;2011/0257416; and 2011/0245542 (all to Cortright and Blommel, andentitled “Synthesis of Liquid Fuels and Chemicals from OxygenatedHydrocarbons”); U.S. Patent Publication No. 2009/0211942 (to Cortright,and entitled “Catalysts and Methods for Reforming OxygenatedCompounds”); U.S. Patent Publication No. 2010/0076233 (to Cortright etal., and entitled “Synthesis of Liquid Fuels from Biomass”);International Patent Application No. PCT/US2008/056330 (to Cortright andBlommel, and entitled “Synthesis of Liquid Fuels and Chemicals fromOxygenated Hydrocarbons”); and commonly owned co-pending InternationalPatent Application No. PCT/US2006/048030 (to Cortright et al., andentitled “Catalyst and Methods for Reforming Oxygenated Compounds”), allof which are incorporated herein by reference.

One drawback of catalytic technologies is the possible negative effectsof water, contaminants, and other residual products on the performanceof the catalyst. For instance, ash components (e.g., calcium, aluminum,potassium, sodium, magnesium, ammonium, chloride, sulfate, sulfite,thiol, silica, copper, iron, phosphate, carbonate, and phosphorous),color bodies (e.g., terpenoids, stilbenes, and flavonoids),proteinaceous materials, and other inorganic or organic products frombiomass conversion can interact with the catalyst to severely limit itsactivity. More complex polysaccharides, such as raw cellulose andhemicellulose, as well as lignin, and their complex degradationproducts, have also proven to be difficult to convert due to their sizeand inability to interact with the catalyst. Therefore, a process forgenerating fuels and chemicals and other hydrocarbons and oxygenatedhydrocarbons from more complex biomass components would be beneficial.It would also be beneficial to improve the efficiency of such processesby minimizing the number of reaction steps, and thus reactors, necessaryto perform the conversion process.

SUMMARY

The invention provides methods for making biomass-derived fuels andchemicals. The method generally involves: (1) providing a biomass feedstream comprising a solvent and a biomass component comprisingcellulose, hemicellulose or lignin; (2) catalytically reacting thebiomass feed stream with hydrogen and a deconstruction catalyst at adeconstruction temperature and a deconstruction pressure to produce aproduct stream comprising a vapor phase, a liquid phase and a solidphase, the vapor phase comprising one or more volatile C₂₊O₁₋₂oxygenates, the liquid phase comprising water and one or more C₂₊O₂₊oxygenated hydrocarbons, and the solid phase comprising extractives; (3)separating the volatile C₂₊O₁₋₂ oxygenates from the liquid phase andsolid phase; and (4) catalytically reacting the volatile C₂₊O₁₋₂oxygenates in the presence of a condensation catalyst at a condensationtemperature and condensation pressure to produce a C₄₊ compoundcomprising a member selected from the group consisting of C₄₊ alcohol,C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene,aryl, fused aryl, and a mixture thereof. In one embodiment, thedeconstruction temperature is between about 120° C. to 350° C. Inanother embodiment, the deconstruction pressure is between about 300 psito 2500 psi.

One aspect of the invention is the composition of the solvent. In oneembodiment, the solvent includes one or more members selected from thegroup consisting of water, in situ generated C₂₊O₂₊ oxygenatedhydrocarbons, recycled C₂₊O₂₊ oxygenated hydrocarbons, bioreformingsolvents, organic solvents, organic acids, and a mixture thereof.

In another embodiment, the biomass component comprises at least onemember selected from the group including recycled fibers, corn stover,bagasse, switch grass, miscanthus, sorghum, wood, wood waste,agricultural waste, algae, and municipal waste.

The deconstruction catalyst may comprise an acidic or basic support, ora support and a member selected from the group consisting of Ru, Co, Rh,Pd, Ni, Mo, and alloys thereof. In another embodiment, thedeconstruction catalyst may further comprise a member selected from thegroup consisting of Pt, Re, Fe, Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti,Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and alloysthereof. In yet another embodiment, the support comprises a memberselected from the group consisting of a nitride, carbon, silica,alumina, zirconia, titania, vanadia, ceria, boron nitride,heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia,zeolites, tungstated zirconia, titania zirconia, sulfated zirconia,phosphated zirconia, acidic alumina, silica-alumina, sulfated alumina,phosphated alumina, and mixtures thereof. In a further embodiment, thesupport is modified by treating the support with a modifier selectedfrom the group consisting of tungsten, titania, sulfate, phosphate, orsilica.

Another aspect of the invention is a solid phase. In one embodiment, thesolid phase further comprises the deconstruction catalyst. In yetanother embodiment, the deconstruction catalyst is separated from theliquid phase; washed in one or more washing medium; regenerated in thepresence of oxygen or hydrogen, at a regenerating pressure and aregenerating temperature wherein carbonaceous deposits are removed fromthe deconstruction catalyst; and then reintroduced to react with thebiomass feed stream.

In one embodiment the washing medium comprises a liquid selected fromthe group consisting of water, an acid, a base, a chelating agent,alcohols, ketones, cyclic ethers, hydroxyketones, aromatics, alkanes,and combinations thereof. In another embodiment, the washing of thedeconstruction catalyst comprises a first step of washing thedeconstruction catalysts with a first washing solvent and a second stepof washing the deconstruction catalyst with a second washing solvent. Inyet another embodiment, the first washing solvent comprises a liquidselected from the group consisting of water, an acid, a base, achelating agent, and combinations thereof, and the second washingsolvent comprises a liquid selected from the group consisting ofalcohols, ketones, cyclic ethers, hydroxyketones, aromatics, alkanes,and combinations thereof. In yet another embodiment, the first washingsolvent comprises a liquid selected from the group consisting ofalcohols, ketones, cyclic ethers, hydroxyketones, aromatics, alkanes,and combinations thereof, and the second washing solvent comprises aliquid selected from the group consisting of water, an acid, a base, achelating agent, and combinations thereof.

In one embodiment, the deconstruction catalyst is regenerated at atemperature of in the range of about 120° C. to about 450° C., and isadjusted at a rate of about 20° C. per hour to about 60° C. per hour. Inanother embodiment, regeneration of the deconstruction catalyst furthercomprises providing a gas stream comprising an inert gas and oxygen, theinert gas provided at a gas flow of between 600-1200 ml gas/ml catalystper hour and the oxygen provided at a concentration of 0.5-10% of thegas stream. In yet another embodiment, regeneration results in removalof more than 90% of the carbonaceous deposits from the deconstructioncatalyst.

The catalytic reaction of the volatile C₂₊O₁₋₂ oxygenates takes place inthe presence of a condensation catalyst. In one embodiment thecondensation catalyst comprises a metal selected from the groupconsisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy thereof, and a combinationthereof. In another embodiment, the condensation catalyst furthercomprises a modifier selected from the group consisting of Ce, La, Y,Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi, and a combination thereof.In yet another embodiment, the condensation catalyst comprises a memberselected from the group consisting of an acidic alumina, aluminumphosphate, silica-alumina phosphate, amorphous silica-alumina, sulfatedalumina, theta alumina, aluminosilicate, zeolites, zirconia, sulfatedzirconia, tungstated zirconia, titania zirconia, phosphated zirconia,tungsten carbide, molybdenum carbide, titania, sulfated carbon,phosphated carbon, phosphated silica, phosphated alumina, acidic resin,heteropolyacid, inorganic acid, and a combination thereof.

The catalytic reaction of the volatile C₂₊O₁₋₂ oxygenates in thepresence of a condensation catalyst produces a C₄₊ compound. In oneembodiment, the C₄₊ compound is benzene, toluene or xylene.

The biomass feed stream is catalytically reacted with the deconstructioncatalyst in the presence of hydrogen. In one embodiment, the hydrogen isselected from the group consisting of external hydrogen, recycledhydrogen or in situ generated hydrogen. In another embodiment, the insitu generated hydrogen is derived from the C₂₊O₂₊ oxygenatedhydrocarbons.

The invention also provides a method of generating a product mixturecomprising two or more C₄₊ compounds. The method generally involves: (1)providing a biomass feed stream comprising a solvent and a biomasscomponent comprising cellulose, hemicellulose or lignin; (2)catalytically reacting the biomass feed stream with hydrogen and adeconstruction catalyst at a deconstruction temperature and adeconstruction pressure to produce a product stream comprising a vaporphase, a liquid phase and a solid phase, the vapor phase comprising oneor more volatile C₂₊O₁₋₂ oxygenates, the liquid phase comprising waterand one or more C₂₊O₂₊ oxygenated hydrocarbons, and the solid phasecomprising extractives; (3) separating the volatile C₂₊O₁₋₂ oxygenatesfrom the liquid phase and solid phase; (4) catalytically reacting thevolatile C₂₊O₁₋₂ oxygenates in the presence of a condensation catalystat a condensation temperature and condensation pressure to produce aproduct mixture comprising two or more C₄₊ compounds selected from thegroup consisting of a C₄₊ alcohol, a C₄₊ ketone, a C₄₊ alkane, a C₄₊alkene, a C₅₊ cycloalkane, a C₅₊ cycloalkene, a aryl, and a fused aryl;and (5) distilling the product mixture to provide a composition selectedfrom the group consisting of an aromatic fraction, a gasoline fraction,a kerosene fraction and a diesel fraction.

In one embodiment, the aromatic fraction comprises benzene, toluene orxylene. In another embodiment, the gasoline fraction has a final boilingpoint in the range of from 150° C. to 220° C., a density at 15° C. inthe range of from 700 to 890 kg/m³, a RON in the range of from 80 to110, and a MON in the range of from 70 to 100. In yet anotherembodiment, the kerosene fraction has an initial boiling point in therange of from 120° C. to 215° C., a final boiling point in the range offrom 220° C. to 320° C., a density at 15° C. in the range of from 700 to890 kg/m³, a freeze point of −40° C. or lower, a smoke point of at least18 mm, and a viscosity at −20° C. in the range of from 1 to 10 cSt. Andin yet another embodiment, the diesel fraction has a T95 in the range offrom 220° C. to 380° C., a flash point in the range of from 30° C. to70° C., a density at 15° C. in the range of from 700 to 900 kg/m³, and aviscosity at 40° C. in the range of from 0.5 to 6 cSt.

The invention also provides a method for generating C₄₊ compounds from abiomass feed stream comprising cellulose, hemicellulose, and lignin. Themethod generally involves: (1) providing a biomass feed streamcomprising a solvent and a biomass component, the solvent comprising oneor more members selected from the group consisting of water, in situgenerated C₂₊O₂₊ oxygenated hydrocarbons, recycled C₂₊O₂₊ oxygenatedhydrocarbons, bioreforming solvents, organic solvents, organic acids,and a mixture thereof, and the biomass component comprising cellulose,hemicellulose and lignin; (2) catalytically reacting the biomass feedstream with hydrogen and a deconstruction catalyst at a deconstructiontemperature and a deconstruction pressure to produce a product streamcomprising a vapor phase, a liquid phase and a solid phase, the vaporphase comprising one or more volatile C₂₊O₁₋₂ oxygenates, the liquidphase comprising water and one or more C₂₊O₂₊ oxygenated hydrocarbons,the solid phase comprising extractives, and the deconstruction catalystcomprising a support and a first member selected from the groupconsisting of Ru, Co, Rh, Pd, Ni, Mo, and alloys thereof, and at leastone additional member selected from the group consisting of Pt, Re, Fe,Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au,Sn, Ge, P, Al, Ga, In, Tl, and alloys thereof; (3) separating thevolatile C₂₊O₁₋₂ oxygenates from the liquid phase and solid phase; and(4) catalytically reacting the volatile C₂₊O₁₋₂ oxygenates in thepresence of a condensation catalyst at a condensation temperature andcondensation pressure to produce a C₄₊ compound comprising a memberselected from the group consisting of C₄₊ alcohol, C₄₊ ketone, C₄₊alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene, aryl, fused aryl,and a mixture thereof.

Other aspects of the invention include: (1) a chemical compositioncomprising a C₄₊ compound derived from any of the foregoing methods; (2)a chemical composition comprising a C₄₊ compound derived from any of theforegoing methods, wherein the C₄₊ compound is benzene, toluene orxylene; (3) a chemical composition comprising a gasoline fractionderived from any of the foregoing methods; (4) a chemical compositioncomprising a kerosene fraction derived from any of the foregoingmethods; and (5) a chemical composition comprising a diesel fractionderived from any of the foregoing methods.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram illustrating one embodiment of the presentinvention.

FIG. 2 is an illustration of one exemplary reaction pathway for theconversion of biomass according to the present invention.

FIG. 3 is a graph providing data for the conversion of a biomass feedstream containing microcrystalline cellulose (MCC) according to thepresent invention.

FIGS. 4 a and 4 b are graphs providing the most abundant aqueous productspeciation and identified aqueous product distribution, respectively,from the conversion of a biomass feed stream containing MCC according tothe present invention.

FIG. 5 is a graph providing the identified aqueous oxygenatedistribution from the conversion of a biomass feed stream containing MCCaccording to the present invention.

FIG. 6 is a graph providing the distribution of the condensable organicvapor phase derived from the conversion of a biomass feed streamcontaining MCC according to the present invention.

FIG. 7 is a graph illustrating the analysis of non-condensable gaseousproducts from the conversion of a biomass feed stream containing MCCaccording to the present invention.

FIG. 8 is a graph providing data for the conversion of a biomass feedstream containing loblolly pine according to the present invention.

FIGS. 9 a and 9 b are graphs providing the most abundant aqueous productspeciation and the identified aqueous product distribution,respectively, from the conversion of a biomass feed stream containingloblolly pine according to the present invention.

FIG. 10 is a graph providing the identified aqueous oxygenatedistribution from the conversion of a biomass feed stream containingloblolly pine according to the present invention.

FIG. 11 is a graph illustrating the analysis of non-condensable gaseousproducts from the conversion of a biomass feed stream containingloblolly pine according to the present invention.

FIG. 12 is a process flow diagram illustrating one of several processconfigurations for conducting the condensation reactions according tothe present invention.

FIG. 13 is a graph providing the product yields from the conversion ofvolatile C₂₊O₁₋₂ oxygenates over a Pd:Ag condensation catalyst.

FIG. 14 is a graph providing the distillation curve for the gasolinefraction derived from the conversion of volatile C₂₊O₁₋₂ oxygenates overa Pd:Ag condensation catalyst.

FIG. 15 is a graph providing the distillation curve for the kerosenefraction derived from the conversion of volatile C₂₊O₁₋₂ oxygenates overa Pd:Ag condensation catalyst.

FIG. 16 is a graph providing the distillation curve for the dieselfraction derived from the conversion of volatile C₂₊O₁₋₂ oxygenates overa Pd:Ag condensation catalyst.

FIG. 17 is a graph providing the total organic carbon (TOC) in theliquid phase from the conversion of a biomass feed stream containingcorn stover with recycle according to the present invention.

FIG. 18 is a graph providing the identified aqueous product distributionof the volatile and bottoms from the conversion of a biomass feed streamcontaining corn stover with recycle according to the present invention.

FIG. 19 is a graph providing the TOC from the conversion of a biomassfeed stream containing corn stover with recycle according to the presentinvention.

FIG. 20 is a graph providing the identified aqueous product distributionof the volatiles and bottoms from the conversion of a biomass feedstream containing corn stover with liquid phase recycle according to thepresent invention.

FIG. 21 is a graph providing the most abundant aqueous productspeciation from the conversion of a biomass feed stream containing cornstover with liquid phase recycle according to the present invention.

FIG. 22 is a graph providing identified condensable organic productspresent in the vapor phase from the deconstruction of a biomass feedstream containing corn stover according to the present invention.

FIG. 23 is a graph providing the identified aqueous product distributionfrom the deconstruction of a biomass feed stream containing MCC undertwo different processing conditions according to the present invention.

FIG. 24 is a graph providing the most abundant aqueous productspeciation from the deconstruction of a biomass feed stream containingMCC under two different processing conditions according to the presentinvention.

FIG. 25 is a flow diagram illustrating one embodiment of the presentinvention.

FIG. 26 is a process flow diagram illustrating one of several processconfigurations for conducting the condensation reactions to producearomatics according to the present invention.

FIG. 27 is a graph providing the carbon number distribution foraromatics produced from the deconstruction of a biomass feed streamcontaining MCC according to the present invention.

FIG. 28 is a graph providing the conversion data for three biomass feedstreams according to the present invention.

FIG. 29 is a graph providing the identified aqueous product distributionfor the conversion of a biomass feed stream containing loblolly pineunder different conditions according to the present invention.

FIG. 30 is a graph providing the identified aqueous product distributionfor the conversion of a biomass feed stream containing corn stover underdifferent conditions according to the present invention.

FIG. 31 is a graph providing the identified aqueous product distributionfor the conversion of a biomass feed stream containing bagasse underdifferent conditions according to the present invention.

FIG. 32 is a graph providing representative condensable organic productspresent in the vapor phase from the deconstruction of a biomass feedstream according to the present invention.

FIG. 33 is a graph providing conversion data of a biomass feed streamcontaining bagasse using various deconstruction catalysts according tothe present invention.

FIG. 34 is a graph providing the identified aqueous liquid phase productdistribution for the deconstruction of a biomass feed stream containingbagasse using various deconstruction catalysts according to the presentinvention.

FIG. 35 is a graph providing the identified aqueous condensable productdistribution present in the vapor phase for the deconstruction of abiomass feed stream containing bagasse using various deconstructioncatalysts according to the present invention.

FIG. 36 is a graph providing representative condensable organic productspresent in the vapor phase from the deconstruction of a biomass feedstream containing bagasse using various deconstruction catalystsaccording to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to methods, reactor systems, and catalystsfor converting biomass to liquid fuels and chemicals in a batch and/orcontinuous process. The invention includes methods of converting bothwater-insoluble and water-soluble components of biomass to volatileoxygenated hydrocarbons, such as C₂₊O₁₋₂ alcohols, ketones, cyclicethers, esters, carboxylic acids, aldehydes, and mixtures thereof. Incertain applications, the volatile oxygenated hydrocarbons can becollected and used as a final chemical product, or used in downstreamprocesses to produce liquid fuels, chemicals and other products.

As used herein, the term “biomass” refers to, without limitation,organic materials produced by plants (e.g., wood, leaves, roots, seeds,stalks, etc.), and microbial and animal metabolic wastes. Common biomasssources include: (1) agricultural residues, such as corn stalks, straw,seed hulls, sugarcane leavings, bagasse, nutshells, and manure fromcattle, poultry, and hogs; (2) wood materials, such as wood or bark,sawdust, timber slash, and mill scrap; (3) municipal waste, such aswaste paper and yard clippings; (4) energy crops, such as poplars,willows, switch grass, miscanthus, sorghum, alfalfa, prairie bluestream,corn, soybean, and the like; (5) residual solids from industrialprocesses, such as lignin from pulping processes, acid hydrolysis orenzymatic hydrolysis; and (6) algae-derived biomass, includingcarbohydrates and lipids from microalgae (e.g., Botryococcus braunii,Chlorella, Dunaliella tertiolecta, Gracilaria, Pleurochyrsis carterae,and Sargassum) and macroalgae (e.g., seaweed). The term also refers tothe primary building blocks of the above, namely, lignin, cellulose,hemicellulose and carbohydrates, such as saccharides, sugars andstarches, among others.

As used herein, the term “bioreforming” refers to, without limitation,processes for catalytically converting biomass to lower molecular weighthydrocarbons and oxygenated compounds, such as alcohols, ketones, cyclicethers, esters, carboxylic acids, aldehydes, diols and other polyols,using heterogeneous catalysts. Bioreforming also includes the furthercatalytic conversion of such lower molecular weight oxygenated compoundsto C₄₊ compounds.

The deconstruction catalysts used herein demonstrate increased toleranceto conditions and species that are typically deleterious to catalystactivity. These species may include ash components (e.g., calcium,aluminum, potassium, sodium, magnesium, ammonium, chloride, sulfate,sulfite, thiol, silica, copper, iron, phosphate, carbonate, andphosphorous), color bodies (e.g., terpenoids, stilbenes, andflavonoids), proteinaceous materials, and other inorganic or organicproducts. In combination with the solvents and reactor conditionsdescribed herein, the deconstruction catalysts also demonstrateincreased activity for the conversion of more complex polysaccharides,such as raw cellulose and hemicellulose, as well as lignin, and theircomplex degradation products.

In the present invention, the principal components of biomass (lignin,cellulose and hemicellulose) are converted to volatile oxygenatedhydrocarbons (referred to herein as volatile oxygenates and/or C₂₊O₁₋₂oxygenates) using hydrogen, a solvent, and a heterogeneousdeconstruction catalyst in a continuous process. An exemplary embodimentof the present invention is illustrated in FIG. 1. A biomass feed streamis created by combining solid biomass that has been chopped, shredded,pressed, ground or processed to a size amenable for conversion, with asolvent (e.g., water, in situ generated C₂₊O₂₊ oxygenated hydrocarbons,recycled C₂₊O₂₊ oxygenated hydrocarbons, bioreforming solvents, organicsolvents, organic acids, and a mixtures thereof). The feed stream isthen passed into a reactor where it reacts with hydrogen and thedeconstruction catalyst at a deconstruction temperature and adeconstruction pressure to cause a reaction that converts all or atleast a portion of the lignin, cellulose, and hemicellulose in thebiomass to a product stream that includes a vapor phase containing oneor more volatile oxygenates, a liquid phase containing a solution ormixture of oxygenated hydrocarbons, and a solid phase containingextractives and, in certain applications, unreacted or under-reactedbiomass and/or the deconstruction catalyst.

Alternatively, a biomass feed stream is created by adding solid biomassthat has been chopped, shredded, pressed, ground or processed to a sizeamenable for conversion, to a reactor containing a solvent, i.e. in anon-slurry form. The solvent (e.g., water, in situ generated C₂₊O₂₊oxygenated hydrocarbons, recycled C₂₊O₂₊ oxygenated hydrocarbons,bioreforming solvents, organic solvents, organic acids, or mixturesthereof) interacts with the solid biomass, thereby making it accessiblefor reaction with hydrogen and the deconstruction catalyst at adeconstruction temperature and a deconstruction pressure. The reactionconverts all or at least a portion of the lignin, cellulose, andhemicellulose in the biomass to a product stream that includes a vaporphase containing one or more volatile oxygenates, a liquid phasecontaining a solution or mixture of C₂₊O₂₊ oxygenated hydrocarbons (aportion of which serves as the solvent), and a solid phase containingextractives and, in certain applications, unreacted or under-reactedbiomass and/or the deconstruction catalyst.

In a liquefaction reactor, as illustrated in FIG. 1, biomass (e.g.,solid biomass or biomass slurry) is initially deconstructed to produce asolution and/or mixture of oxygenated hydrocarbons, such ashemicellulose, cellulose, polysaccharides, oligosaccharides, sugars,sugar alcohols, sugar degradation products, depolymerized lignincompounds, and the like. As these components are exposed to thedeconstruction catalyst and hydrogen, the oxygen content of thecompounds is reduced (see FIG. 2) to provide both volatile oxygenatesand C₂₊O₂₊ oxygenated hydrocarbons. The C₂₊O₂₊ oxygenated hydrocarbonsform an in situ generated solvent within the reactor that, in turn: 1)enhances biomass deconstruction, 2) improves the solubility of thedeconstructed biomass components—particularly the lignin derivedcomponents—to facilitate reaction with the catalyst, and 3) is furtherdeoxygenated to produce the desired volatile oxygenates. The volatileoxygenates then exit the deconstruction reactor as a condensable vaporproduct for further processing or use in industrial chemicals. Residualoxygenated hydrocarbons can also exit the deconstruction reactor as aliquid phase and be recycled back to the reactor for further conversionand/or use as a solvent or separated for further processing or use asindustrial chemicals.

The composition of the phases of the product stream will vary dependingon the process conditions and the particular type of biomass feedstockemployed. The vapor phase will generally contain volatile oxygenates,hydrogen, carbon monoxide, carbon dioxide, and light alkanes. As usedherein, volatile oxygenates refers to oxygenated hydrocarbons having arelative volatility (α) with respect to 1-hexanol of greater than 0.03based on pure components at 250° C. The volatile oxygenates willgenerally include mono-oxygenated hydrocarbons and di-oxygenatedhydrocarbons (collectively referred to herein as C₂₊O₁₋₂ oxygenates), aswell as residual oxygenated compounds capable of being volatilized basedon the temperature, total pressure, and concentration of the compounds.Mono-oxygenated hydrocarbons generically refers to hydrocarbon compoundshaving 2 or more carbon atoms and 1 oxygen atom (referred to herein asC₂₊O₁ hydrocarbons), such as alcohols, ketones, aldehydes, ethers,cyclic ethers, and furans. Di-oxygenated hydrocarbons generically refersto hydrocarbon compounds having 2 or more carbon atoms and 2 oxygenatoms (referred to herein as C₂₊O₂ hydrocarbons), and may include,without limitations, diols, di-oxygenated ketones, and organic acids.Residual oxygenated compounds may include components containing three ormore oxygen atoms, such as glycerol, which are volatilized due to theprocessing conditions and their concentration in the reaction stream.

The volatile oxygenates will generally have greater than 2 or greaterthan 3 carbon atoms, and less than 10 or less than 6 carbon atoms.Preferably, the volatile oxygenates have from 2 to 10 carbon atoms, or 2to 6 carbon atoms, or 3 to 6 carbon atoms. Volatile oxygenates that arealcohols may include, without limitation, primary, secondary, linear,branched or cyclic C₂₊ alcohols, such as ethanol, n-propyl alcohol,isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol,cyclopentanol, hexanol, cyclohexanol, methyl-cyclohexanol,ethyl-cyclohexanol, propyl-cyclohexanol, 2-methyl-cyclopentanonol,heptanol, octanol, nonanol, decanol, undecanol, dodecanol, and isomersthereof. The alcohols may also include phenols and alkyl substitutedphenols, such as methyl, ethyl and propyl phenols, and ortho-, meta-,para-cresols. Volatile ketone oxygenates may include, withoutlimitation, cyclic ketones, aromatic ketones, acetone, propanone,butanone, pentanone, cyclopentanone, hexanone, cyclohexanone,acetophenone, 2-methyl-cyclopentanone, heptanone, octanone, nonanone,decanone, undecanone, dodecanone, and isomers thereof, as well asdi-oxygenated ketones, such as hydroxyketones, diketones,butane-2,3-dione, 3-hydroxybutan-2-one, pentane-2,3-dione,pentane-2,4-dione, 2-oxopropanal, methylglyoxal, butanedione,pentanedione, diketohexane, and isomers thereof. The aldehydes mayinclude, without limitation, pentanal, acetaldehyde, hydroxyaldehydes,propionaldehyde, butyraldehyde, hexanal, heptanal, octanal, nonal,decanal, undecanal, dodecanal, and isomers thereof. The ethers mayinclude, without limitation, ethers, such as diethyl ether, diisopropylether, 2-ethylhexyl ether, methylethyl ether, ethylpropyl ether, andmethylpropyl ether. The cyclic ethers may include, without limitation,tetrahydrofuran, 2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran,2-ethyl-tetrahydrofuran, and isomers thereof, as well as di-oxygenatedcyclic ethers, such as 3-hydroxytetrahydrofuran, tetrahydro-3-furanol,tetrahydrofurfuryl alcohol, 1-(2-furyl)ethanol, furan, dihydrofuran,2-furan methanol, 2-methyl furan, 2-ethyl furan, 2,5-dimethyl furan, andisomers thereof. The light carboxylic acids may include, withoutlimitation, formic acid, acetic acid, and propionic acid. The volatileoxygenates may also include small amounts of the heavy organic acids,diols, triols, phenols, cresols and other polyols referenced in thefollowing paragraph, to the extent they are volatilized to the vaporphase due to the particular processing conditions, their concentrationswithin the reaction stream, and azeotropic behavior.

The liquid phase will generally include water and C₂₊O₂₊ oxygenatedhydrocarbons not volatilized to the vapor phase, such as ligninderivatives, disaccharides, monosaccharides, sugars, sugar alcohols,alditols, heavy organic acids, phenols, cresols, and heavy diols, triolsand other polyols. As used herein, C₂₊O₂₊ oxygenated hydrocarbonsgenerally refers to oxygenated hydrocarbons having 2 or more carbonatoms and 2 or more oxygen atoms, and having a relative volatility (α)with respect to 1-hexanol of less than 0.03 based on pure components at250° C. The C₂₊O₂₊ oxygenated hydrocarbons may also include smallamounts of the C₂₊O₂ hydrocarbons, to the extent the C₂₊O₂ hydrocarbonsare not volatilized to the vapor phase due to the particular processingconditions, their concentrations within the reaction stream, andazeotropic behavior. Preferably, the C₂₊O₂₊ oxygenated hydrocarbons have2 to 6 carbon atoms or 2 to 12 carbon atoms. The C₂₊O₂₊ oxygenatedhydrocarbons may also have 2 or more carbon atoms, 6 or more carbonatoms, 18 or more carbon atoms, or 24 or more carbon atoms, depending onthe processing conditions and their concentration in the reactionstream. Exemplary C₂₊O₂ hydrocarbon species that may be present in boththe liquid and vapor phases include hydroxyacetone, ethylene glycol,propylene glycol, and organic acids (e.g., acetic acid, propionic acid,lactic acid, etc.).

The C₂₊O₂₊ oxygenated hydrocarbons will generally be soluble in waterand/or a solvent, but may also include compounds that are insoluble inwater. In one embodiment, the C₂₊O₂₊ oxygenated hydrocarbons includesugars, sugar alcohols, sugar degradation products, starch, saccharidesand other polyhydric alcohols. Preferably, the C₂₊O₂₊ oxygenatedhydrocarbons include a sugar, such as glucose, fructose, sucrose,maltose, lactose, mannose or xylose, or a sugar alcohol, such asarabitol, erythritol, glycerol, isomalt, lactitol, maltitol, mannitol,sorbitol, xylitol, arabitol, or glycol. In other embodiments, the C₂₊O₂₊oxygenated hydrocarbons may also include esters, heavy carboxylic acids,diols and other polyols. The organic acids may include, withoutlimitation, butanoic acid, pentanoic acid, hexanoic acid, heptanoicacid, isomers and derivatives thereof, including hydroxylatedderivatives, such as 2-hydroxybutanoic acid and lactic acid. The diolsmay include, without limitation, ethylene glycol, propylene glycol,1,3-propanediol, butanediol, pentanediol, hexanediol, heptanediol,octanediol, nonanediol, decanediol, undecanediol, dodecanediol,dihydroxy benzene, catechol, resorcinol, cyclic diols, substitutesthereof, and isomers thereof. The triols may include, withoutlimitation, glycerol, 1,1,1 tris(hydroxymethyl)-ethane(trimethylolethane), trimethylolpropane, hexanetriol, and isomersthereof. Other tri-oxygenates may include, without limitation,tetrahydro-2-furoic acid, hydroxymethyltetrahydrofurfural,hydroxylmethylfurfural, dihydro-5-(hydroxymethyl)-2(3H)-furanone,5-hydroxymethyl-2(5H)-furanone,dihydro-5-(hydroxymethyl)-2(3H)-furanone, and isomers thereof. Theliquid phase may also include volatile oxygenates, including any of thealcohols, ketones, aldehydes, carboxylic acids, ethers and cyclic ethersreferenced above, to the extent they are present in the liquid phase.

The solid phase will generally include extractives and unreacted orunder-reacted biomass and, in certain applications, the deconstructioncatalyst. Extractives will typically include ash components, such ascalcium, aluminum, potassium, sodium, magnesium, chloride, sulfates,sulfites, thiols, silica, copper, iron, phosphates, and phosphorous, aswell as color bodies (e.g., terpenoids, stilbenes, flavonoids),proteinaceous materials and other inorganic products. The under-reactedbiomass will typically include partially reacted biomass, and otherheavy lignin, cellulose and hemicellulose derivatives not readilysolubilized or maintained in a liquid phase, such as heavypolysaccharides, starches, and other longer chain oxygenatedhydrocarbons.

The volatile oxygenates can undergo condensation reactions to formeither larger carbon number straight chain compounds, branched chaincompounds, or cyclic compounds. The resulting compounds may behydrocarbons or hydrocarbons containing oxygen, the oxygen of which canbe removed through the reaction with hydrogen over a catalyst. Theresulting condensed products include C₄₊ alcohols, C₄₊ ketones, C₄₊alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊ cycloalkenes, aryls, fusedaryls, and mixtures thereof. The mixtures can be fractionated and/orblended to produce the appropriate mixtures of molecules typically usedin gasoline, jet fuel, diesel fuel, or in industrial chemical processes.

Following conversion over the deconstruction catalyst, the productstream undergoes one or more separation steps to separate the vapor,liquid and solid phase components. Various separation techniques areknown in the art and may be used. Such techniques may include, withoutlimitation, gravitational settling techniques, cyclone separationtechniques, simulated moving bed technology, distillation, filtration,etc. In one embodiment, the reactor system may include an outlet for thecapture and removal of the vapor phase, and a second outlet for thecollection and removal of the liquid phase and solid phase components.In another embodiment, the product stream can be directed into a phaseseparator to allow for the simultaneous separation of each phase of theproduct stream. In either application, the liquid and solid phase can bedirected into a settling tank configured to allow a bottom portioncontaining solid materials (e.g., catalyst, extractives and unreacted orunder-reacted materials) to separate from a top liquid phase portioncontaining a significant fraction of the C₂₊O₂₊ oxygenated hydrocarbons.In certain embodiments, a portion of the liquid phase may also bemaintained in the bottom portion to assist with the movement of thesolid materials through additional processing steps or recycled to thebiomass feed stream for use as a solvent to aid in biomassdeconstruction.

In certain embodiments, the liquid phase may also require furtherprocessing to separate aqueous phase products from organic phaseproducts, such as lignin-based hydrocarbons that are not suitable forfurther conversion. The liquid phase may also be dewatered or furtherpurified prior to being introduced into further processing steps. Suchdewatering and purification processes are known in the art and mayinclude techniques such as distillation, filtration, etc.

In one embodiment, the resulting solution of C₂₊O₂₊ oxygenatedhydrocarbons is collected for further processing in a bioreformingprocess or, alternatively, used as a feedstock for other conversionprocesses, including the production of fuels and chemicals usingfermentation or enzymatic technologies. For example, water-solublecarbohydrates, such as starch, monosaccharides, disaccharides,polysaccharides, sugars, and sugar alcohols, and water-solublederivatives from the lignin, hemicellulose and cellulose are suitablefor use in bioreforming processes, such as those described in U.S. Pat.Nos. 6,699,457; 6,964,757; 6,964,758; and 7,618,612 (all to Cortright etal., and entitled “Low-Temperature Hydrogen Production from OxygenatedHydrocarbons”); U.S. Pat. No. 6,953,873 (to Cortright et al., andentitled “Low-Temperature Hydrocarbon Production from OxygenatedHydrocarbons”); U.S. Pat. Nos. 7,767,867; 7,989,664; and U.S. PatentPublication No. 2011/0306804 (to Cortright, and entitled “Methods andSystems for Generating Polyols”); U.S. Pat. Nos. 8,053,615; 8,017,818;7,977,517; and U.S. Patent Publication Nos. 2011/0257448; 2011/0245543;2011/0257416; and 2011/0245542 (all to Cortright and Blommel, andentitled “Synthesis of Liquid Fuels and Chemicals from OxygenatedHydrocarbons”); U.S. Patent Publication No. 2009/0211942 (to Cortright,and entitled “Catalysts and Methods for Reforming OxygenatedCompounds”); U.S. Patent Publication No. 2010/0076233 (to Cortright etal., and entitled “Synthesis of Liquid Fuels from Biomass”);International Patent Application No. PCT/US2008/056330 (to Cortright andBlommel, and entitled “Synthesis of Liquid Fuels and Chemicals fromOxygenated Hydrocarbons”); and commonly owned co-pending InternationalPatent Application No. PCT/US2006/048030 (to Cortright et al., andentitled “Catalyst and Methods for Reforming Oxygenated Compounds”), allof which are incorporated herein by reference. Alternatively, the liquidphase may be recycled and combined in the biomass feed stream forfurther conversion.

Biomass Deconstruction

To produce the desired products, the biomass feed stream is reacted withhydrogen over a heterogeneous deconstruction catalyst under conditionsof temperature and pressure effective to convert the lignin, cellulose,hemicellulose and their derivatives, whether recycled or reactivelygenerated in the feed stream, to a product stream containing volatileC₂₊O₁₋₂ oxygenates in a gas phase, and a solution of C₂₊O₂₊ oxygenatedhydrocarbons. The specific products produced will depend on variousfactors including the composition of the feed stream, reactiontemperature, reaction pressure, water and/or solvent concentration,hydrogen concentration, the reactivity of the catalyst, and the flowrate of the feed stream as it affects the space velocity (themass/volume of reactant per unit of catalyst per unit of time), gashourly space velocity (GHSV), liquid hour space velocity (LHSV), andweight hourly space velocity (WHSV). For example, the vapor phase mayalso include small amounts of other compounds (e.g., glycerol, heavyorganic acids, butane diols, butane triols, etc.) due to the processingconditions and their concentration.

The biomass may be originally provided in its native form, pelletized orreduced to a size appropriate for processing, such as by chopping,shredding, or grinding to a size that allows maximum contact with thedeconstruction catalyst or movement through the reactor system. Thebiomass may also be pretreated or washed in water or a solvent to removeall or a portion of the ash, lignin or any undesired componentscontained in the biomass or in the biomass stream. The washing mayinclude hot water extraction or any one or more biological, enzymatic orthermochemical processes, such as enzymatic hydrolysis, acid hydrolysisor organosolv type applications.

The deconstruction catalyst is a heterogeneous catalyst having one ormore materials capable of catalyzing a reaction between hydrogen andlignin, cellulose, hemicellulose and their derivatives to produce thedesired water-soluble oxygenated compounds. The heterogeneous catalystmay include, without limitation, acid modified resins, acid modifiedsupports, base modified resins, base modified supports, tungstencarbides, and/or one or more of Ru, Co, Rh, Pd, Ni, Mo. The catalyst mayalso include these elements alone or combined with one or more Fe, Ir,Pt, Re, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag,Au, Sn, Ge, P, Al, Ga, In, Tl, alloys thereof, and combinations thereof.In one embodiment, the catalyst includes Ru, Co, Rh, Pd, Ni, or Mo andat least one member selected from W, B, Pt, Pd, Sn, Ag, Au, Rh, Co, Re,and Mo.

Resins will generally include basic or acidic supports (e.g., supportshaving low isoelectric points) that are able to catalyze liquefactionreactions of biomass, followed by hydrogenation reactions in thepresence of H₂, leading to carbon atoms that are not bonded to oxygenatoms. One class of acidic supports includes heteropolyacids,solid-phase acids exemplified by such species asH_(3+x)PMo_(12-x)V_(x)O₄₀, H₄SiW₁₂O₄₀, H₃PW₁₂O₄₀, and H₆P₂W₁₈O₆₂.Heteropolyacids also have a well-defined local structure, the mostcommon of which is the tungsten-based Keggin structure. Basic resins mayinclude supports that exhibit basic functionality. Examples of acidicand basic resins include the Amberlyst 15Wet, 15Dry, 16Wet, 31Wet, 33,35Wet, 35Dry, 39Wet, 70, CH10, CH28 resins, Amberlyst A21, A23, A24 andA26 OH resins, and the Amberjet 4200 Cl, Amberlite IRA 400 Cl, AmberliteIRA 410 Cl, Amberlite IRC76, Amberlite IRC747, Amberlite IRC748,Ambersep GT74, Ambersep 820U Cl, resins produced by Rohm Haas.

The catalyst is either self-supporting or includes a supportingmaterial. The support may contain any one or more of nitride, carbon,silica, alumina, acidic alumina, silica-alumina, theta-alumina, sulfatedalumina, phosphated alumina, zirconia, sulfated zirconia, phosphatezirconia, titania zirconia, tungstated zirconia, titania, tungsten,vanadia, ceria, zinc oxide, chromia, boron nitride, heteropolyacids,kieselguhr, hydroxyapatite, and mixtures thereof. Nanoporous supportssuch as zeolites, carbon nanotubes, or carbon fullerene may also beused. Preferable supports are carbon, alumina, phosphate zirconia,m-ZrO₂, and W—ZrO₂. In one embodiment, the deconstruction catalystincludes Ni:Mo, Pd:Mo, Rh:Mo, Pd:Ag or Co:Mo on a m-ZrO₂ support. Inanother embodiment, the catalyst includes Ru, Ru:Pt, Ru:Pd, Pd:Ag, orRu:Pt:Sn on a carbon or W—ZrO₂ support. The support may also serve as afunctional catalyst, such as in the case of acidic or basic resins orsupports having acidic or basic functionality.

The deconstruction catalyst may be designed and configured to functionas a fixed bed within a reactor or mixed with the feed stream as in aslurry reactor. In one embodiment, the catalyst is formed in ahoneycombed monolith design such that the biomass feed stream, whetheras a biomass slurry, solid phase slurry, or a solid/liquid phase slurry,can flow through the catalyst. In another embodiment, the catalystincludes a magnetic element, such as Fe or Co, so that the catalyst canbe easily separated from the resulting biomass product stream. In yetanother embodiment, the deconstruction catalyst is a metal spongematerial, such as a sponge nickel catalyst.

Activated sponge nickel catalysts (e.g., Raney nickel) are a well-knownclass of materials effective for various reactions. The Raney nickelcatalyst is typically prepared by treating an alloy of approximatelyequal amounts by weight of nickel and aluminum with an aqueous alkalisolution, e.g., containing about 25 wt. % of sodium hydroxide. Thealuminum is selectively dissolved by the aqueous alkali solution leavingparticles having a sponge construction and composed predominantly ofnickel with a minor amount of aluminum. Promoter metals, such as thosedescribed above, may be included in the initial alloy in an amount suchthat about 1-5 wt. % remains in the sponge nickel catalyst.

The deconstruction process can be either batch or continuous. In oneembodiment, the deconstruction process is a continuous process using oneor more continuous stirred-tank reactors in parallel or in series. Thedeconstruction temperature will generally be greater than 120° C., or150° C., or 185° C., or 200° C., or 250° C., or 270° C., and less than350° C., or 325° C., or 310° C., or 300° C. In one embodiment, thedeconstruction temperature is between about 120° C. and 350° C., orbetween about 150° C. and 325° C., or between about 200° C. and 310° C.,or between about 250° C. and 300° C., or between about 270° C. and 300°C. The deconstruction pressure will generally be greater than 300 psi,or 375 psi, or 475 psi, or 600 psi, or 750 psi, or 1000 psi, and lessthan 2500 psi, or 2400 psi, or 2150 psi, or 1900 psi, or 1750 psi, or1500 psi. In one embodiment the deconstruction pressure is between about300 psi and 2500 psi, or between about 300 psi and 1500 psi, or betweenabout 1000 psi and 1500 psi. In one embodiment, the deconstructionoccurs stage-wise such that the deconstruction temperature anddeconstruction pressure can be varied in each stage (e.g., a first stagedeconstruction temperature and pressure between about 150° C. and 325°C. and between about 300 psi and 1800 psi, respectively, and a secondstage deconstruction temperature and pressure between about 200° C. and300° C. and about 800 psi and 1500 psi, respectively). Collectively, thetemperature and pressure conditions should be such that a significantportion of the volatile C₂₊O₁₋₂ oxygenates are in the vapor phase, whilea significant portion of the water and less-volatile C₂₊O₂₊ oxygenates(e.g., heavier di-oxygenates, tri-oxygenates and other polyoxygenates,etc.) and other lignin, hemicellulose and cellulose derivatives (e.g.,sugars, sugar alcohols, saccharides, starches, etc.) are maintained inthe liquid phase and/or solid phase.

In general, the reaction should be conducted under conditions where theresidence time of the feed stream over the catalyst is appropriate togenerate the volatile C₂₊O₁₋₂ oxygenates in a gas phase. For example,the WHSV for the reaction may be at least about 0.1 gram of biomass pergram of catalyst per hour, and more preferably about 0.1 to 40.0 g/g hr,including a WHSV of about 0.25, 0.5, 0.75, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5,1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9,3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3,4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,20, 25, 30, 35, 40 g/g hr, and ratios between (including 0.83, 0.84,0.85, 1.71, 1.72, 1.73, etc.). Preferably, the biomass feed streamcontacts the catalyst for between approximately 5 minutes and 6 hours.

The present invention is able to effectively convert the biomasscomponents to lower molecular weight oxygenated hydrocarbons due to thepresence of hydrogen in the system. The hydrogen facilitates thereaction and conversion process by immediately reacting with the variousreaction intermediates and the catalyst to produce products that aremore stable and less subject to degradation. The hydrogen may begenerated in situ using aqueous phase reforming (in situ generated H₂ orAPR H₂), whether in the biomass deconstruction reactor or in downstreamprocesses using the water-soluble C₂₊O₂₊ oxygenated hydrocarbons fromthe liquid phase as a feedstock, or a combination of APR H₂, external H₂or recycled H₂, or just simply external H₂ or recycled H₂. The term“external H₂” refers to hydrogen that does not originate from thebiomass solution, but is added to the reactor system from an externalsource. The term “recycled H₂” refers to unconsumed hydrogen which iscollected and then recycled back into the reactor system for furtheruse. External H₂ and recycled H₂ may also be referred to collectively orindividually as “supplemental H₂.” In general, the amount of H₂ addedshould maintain the reaction pressure within the system at the desiredlevels, or to increase the molar ratio of hydrogen to carbon and/oroxygen in order to enhance the production yield of certain reactionproduct types.

The deconstruction process may also include the introduction ofsupplemental materials to the feed stream to assist with the biomassdeconstruction or to increase the yields of the conversion process.Yield increasing supplemental materials may include: unreacted orunder-reacted materials recycled from the solid phase of the productstream; C₂₊O₂₊ oxygenated hydrocarbons from the liquid phase; and/orsolvents from downstream or other processes. Supplemental materials mayalso include conventional feedstock streams (e.g., starches, syrups,carbohydrates, and sugars), which may also be readily converted to thedesired volatile C₂₊O₁₋₂ oxygenates or liquid phase products.

Another supplemental material may include a pressurized gas stream(e.g., hydrogen, inert gas, or product gas) that is sparged through thebiomass and catalyst during the deconstruction process. Sparging is usedto remove desired products from the reactor to prevent unwanted sidereactions (e.g., degradation reactions).

Supplemental materials may also include solvents that aid in thedeconstruction process. Solvent-based applications are well known in theart. Organosolv processes use organic solvents such as ionic liquids,acetone, ethanol, 4-methyl-2-pentanone, and solvent mixtures, tofractionate lignocellulosic biomass into cellulose, hemicellulose, andlignin streams (Paszner 1984; Muurinen 2000; and Bozell 1998).Strong-acid processes use concentrated hydrochloric acid, phosphoricacid, sulfuric acid or other strong organic acids as thedepolymerization agent, while weak acid processes involve the use ofdilute strong acids, acetic acid, oxalic acid, hydrofluoric acid, orother weak acids as the solvent. Enzymatic processes have also recentlygained prominence and include the use of enzymes as a biocatalyst todecrystallize the structure of the biomass and allow further hydrolysisto useable feedstocks. In one example, the supplemental materialsinclude acetone, gluconic acid, acetic acid, H₂SO₄ or H₃PO₄. In anotherexample, the supplemental materials include an aqueous solution ofwater-soluble oxygenated hydrocarbons, and solvents derived from abioreforming process, such as those described in U.S. Pat. Nos.7,767,867; 7,989,664; and U.S. Patent Publication No. 2011/0306804 allto Cortright, and entitled “Methods and Systems for Generating Polyols”.

Condensation

The volatile C₂₊O₁₋₂ oxygenates produced can be collected and used inindustrial applications, or converted into C₄₊ compounds by condensationreactions catalyzed by a condensation catalyst. Without being limited toany specific theories, it is believed that the condensation reactionsgenerally consist of a series of steps involving: (a) the dehydration ofoxygenates to alkenes; (b) oligomerization of the alkenes; (c) crackingreactions; (d) cyclization of larger alkenes to form aromatics; (e)alkane isomerization; (f) hydrogen-transfer reactions to form alkanes.The reactions may also consist of a series of steps involving: (1) aldolcondensation to form a β-hydroxyketone or β-hydroxyaldehyde; (2)dehydration of the β-hydroxyketone or β-hydroxyaldehyde to form aconjugated enone; (3) hydrogenation of the conjugated enone to form aketone or aldehyde, which may participate in further condensationreactions or conversion to an alcohol or hydrocarbon; and (4)hydrogenation of carbonyls to alcohols, or vice-versa. Othercondensation reactions may occur in parallel, including aldolcondensation, prins reactions, ketonization of acids, and Diels-Aldercondensation.

The condensation catalyst will generally be a catalyst capable offorming longer chain compounds by linking two oxygen containing speciesthrough a new carbon-carbon bond, and converting the resulting compoundto a hydrocarbon, alcohol or ketone. The condensation catalyst mayinclude, without limitation, carbides, nitrides, zirconia, alumina,silica, aluminosilicates, phosphates, zeolites, titanium oxides, zincoxides, vanadium oxides, lanthanum oxides, yttrium oxides, scandiumoxides, magnesium oxides, cerium oxides, barium oxides, calcium oxides,hydroxides, heteropolyacids, inorganic acids, acid modified resins, basemodified resins, and combinations thereof. The condensation catalyst mayinclude the above alone or in combination with a modifier, such as Ce,La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinationsthereof. The condensation catalyst may also include a metal, such as Cu,Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo,W, Sn, Os, alloys and combinations thereof, to provide a metalfunctionality.

The condensation catalyst may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or may require aseparate support suitable for suspending the catalyst in the reactantstream. Particularly beneficial supports include alumina, silica, andzirconia. In other embodiments, particularly when the condensationcatalyst is a powder, the catalyst system may include a binder to assistin forming the catalyst into a desirable catalyst shape. Applicableforming processes include extrusion, pelletization, oil dropping, orother known processes. Zinc oxide, alumina, and a peptizing agent mayalso be mixed together and extruded to produce a formed material. Afterdrying, this material is calcined at a temperature appropriate forformation of the catalytically active phase, which usually requirestemperatures in excess of 350° C. Other catalyst supports may includethose described in further detail below.

In one embodiment, the condensation reaction is performed using acatalyst having acidic functionality. The acid catalysts may include,without limitation, aluminosilicates (zeolites), silica-aluminaphosphates (SAPO), aluminum phosphates (ALPO), amorphous silica alumina,zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide,molybdenum carbide, titania, acidic alumina, phosphated alumina,phosphated silica, sulfated carbons, phosphated carbons, acidic resins,heteropolyacids, inorganic acids, and combinations thereof. In oneembodiment, the catalyst may also include a modifier, such as Ce, La, Y,Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi, and combinations thereof.The catalyst may also be modified by the addition of a metal, such asCu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo,W, Sn, Os, alloys and combinations thereof, to provide metalfunctionality, and/or sulfides and oxides of Ti, Zr, V, Nb, Ta, Mo, Cr,W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, P, andcombinations thereof. Tungstated zirconia has been found to be aparticularly useful catalyst for the present process, especially whenmodified with Cu, Pd, Ag, Pt, Ru, Ni, Sn and combinations thereof. Theacid catalyst may be homogenous, self-supporting or adhered to any oneof the supports further described below, including supports containingcarbon, silica, alumina, zirconia, titania, vanadia, ceria,heteropolyacids, alloys and mixtures thereof.

For example, the condensation catalyst may be a zeolite catalyst. Theterm “zeolite” as used herein refers not only to microporous crystallinealuminosilicate, but also microporous crystalline metal-containingaluminosilicate structures, such as galloaluminosilicates andgallosilicates. In such instances, In, Zn, Fe, Mo, Ag, Au, Ni, P, Y, Ta,and lanthanides may be exchanged onto zeolites to provide the desiredactivity. Metal functionality may be provided by metals such as Cu, Ag,Au, Pt, Ni, Fe, Co, Ru, Zn, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os,alloys and combinations thereof.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,702,886; Re. 29,948(highly siliceous ZSM-5); U.S. Pat. Nos. 4,100,262 and 4,139,600, allincorporated herein by reference. Zeolite ZSM-11, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,709,979, which isalso incorporated herein by reference. Zeolite ZSM-12, and theconventional preparation thereof, is described in U.S. Pat. No.3,832,449, incorporated herein by reference. Zeolite ZSM-23, and theconventional preparation thereof, is described in U.S. Pat. No.4,076,842, incorporated herein by reference. Zeolite ZSM-35, and theconventional preparation thereof, is described in U.S. Pat. No.4,016,245, incorporated herein by reference. Another preparation ofZSM-35 is described in U.S. Pat. No. 4,107,195, the disclosure of whichis incorporated herein by reference. ZSM-48, and the conventionalpreparation thereof, is taught by U.S. Pat. No. 4,375,573, incorporatedherein by reference. Other examples of zeolite catalysts are describedin U.S. Pat. No. 5,019,663 and U.S. Pat. No. 7,022,888, alsoincorporated herein by reference. In one embodiment, the condensationcatalyst is a ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Ni, Sn, orcombinations thereof.

As described in U.S. Pat. No. 7,022,888, the condensation catalyst maybe a bifunctional pentasil zeolite catalyst including at least onemetallic element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn,Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc,Ni, P, Ta, lanthanides, and combinations thereof. The zeolite preferablyhas strong acidic sites, and may be used with reactant streamscontaining and an oxygenated hydrocarbon at a temperature of below 580°C. The bifunctional pentasil zeolite may have ZSM-5, ZSM-8 or ZSM-11type crystal structure consisting of a large number of 5-memberedoxygen-rings (i.e., pentasil rings). The zeolite with ZSM-5 typestructure is a particularly preferred catalyst.

The condensation catalyst may include one or more zeolite structurescomprising cage-like structures of silica-alumina. Zeolites arecrystalline microporous materials with well-defined pore structures.Zeolites contain active sites, usually acid sites, which can begenerated in the zeolite framework. The strength and concentration ofthe active sites can be tailored for particular applications. Examplesof suitable zeolites for condensing secondary alcohols and alkanes maycomprise aluminosilicates, optionally modified with cations, such as Ga,In, Zn, Mo, and mixtures of such cations, as described, for example, inU.S. Pat. No. 3,702,886, which is incorporated herein by reference. Asrecognized in the art, the structure of the particular zeolite orzeolites may be altered to provide different amounts of varioushydrocarbon species in the product mixture. Depending on the structureof the zeolite catalyst, the product mixture may contain various amountsof aromatic and cyclic hydrocarbons.

Alternatively, solid acid catalysts such as alumina modified withphosphates, chloride, silica, and other acidic oxides could be used inpracticing the present invention. Also, sulfated zirconia, phosphatedzirconia, titania zirconia, or tungstated zirconia may provide thenecessary acidity. Re and Pt/Re catalysts are also useful for promotingcondensation of oxygenates to C₅₊ hydrocarbons and/or C₅₊mono-oxygenates. The Re is sufficiently acidic to promote acid-catalyzedcondensation. Acidity may also be added to activated carbon by theaddition of either sulfates or phosphates.

The specific C₄₊ compounds produced will depend on various factors,including, without limitation, the type of volatile C₂₊O₁₋₂ oxygenatesin the reactant stream, condensation temperature, condensation pressure,the reactivity of the catalyst, and the flow rate of the reactant streamas it affects the space velocity, GHSV, LHSV, and WHSV. Preferably, thereactant stream is contacted with the condensation catalyst at a WHSVthat is appropriate to produce the desired hydrocarbon products. TheWHSV is preferably at least about 0.1 grams of volatile C₂₊O₁₋₂oxygenates in the reactant stream per gram catalyst per hour, morepreferably the WHSV is between about 0.1 to 10.0 g/g hr, including aWHSV of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g/g hr, and incrementsbetween.

The condensation reaction should be carried out at a temperature andpressure at which the thermodynamics of the proposed reaction arefavorable. In general, the reaction should be carried out at atemperature where the vapor pressure of the volatile C₂₊O₁₋₂ oxygenatesis at least about 0.1 atm (and preferably a good deal higher). Thecondensation temperature will vary depending upon the specificcomposition of the volatile C₂₊O₁₋₂ oxygenates. The condensationtemperature will generally be greater than 80° C., or 125° C., or 175°C., or 200° C., or 225° C., or 250° C., and less than 500° C., or 450°C., or 425° C., or 375° C., or 325° C., or 275° C. In one embodiment,the condensation temperature is between about 80° C. to 500° C., orbetween about 125° C. to 450° C., or between about 250° C. to 425° C.The condensation pressure will generally be greater than 0 psig, or 10psig, or 100 psig, or 200 psig, and less than 1200 psig, or 1100 psig,or 1000 psig, or 900 psig, or 700 psig. In one embodiment, thecondensation pressure is greater than about 0.1 atm, or between about 0and 1200 psig, or between about 0 and 1000 psig.

Varying the factors above, as well as others, will generally result in amodification to the specific composition and yields of the C₄₊compounds. For example, varying the temperature and/or pressure of thereactor system, or the particular catalyst formulations, may result inthe production of C₄₊ alcohols and/or ketones instead of C₄₊hydrocarbons. The C₄₊ hydrocarbon product may also contain a variety ofalkenes, and alkanes of various sizes (including both normal andbranched alkanes). Depending upon the condensation catalyst used, thehydrocarbon product may also include aromatic and cyclic hydrocarboncompounds. The C₄₊ hydrocarbon product may also contain undesirably highlevels of alkenes, which may lead to coking or deposits in combustionengines, or other undesirable hydrocarbon products. In such an event,the hydrocarbon molecules produced may be optionally hydrogenated toreduce the ketones to alcohols and hydrocarbons, while the alcohols andunsaturated hydrocarbon may be reduced to alkanes, cyclic alkanes, andaromatics, thereby forming a more desirable hydrocarbon product havinglow levels of alkenes, aromatics or alcohols.

The finishing step will generally involve a hydrogenation reaction thatremoves the remaining oxygen from the hydrocarbons, including removingoxygen from carbonyls, hydroxyls, furans, acids, esters, phenols.Various processes and catalysts are known for hydrogenating oxygenatedcompounds. Typical catalysts include a support with any one or more ofthe following metals, Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, alloys orcombinations thereof, alone or with promoters such as Au, Ag, Cr, Zn,Mn, Sn, Cu, Bi, and alloys thereof. The above metals and promoters maybe used in various loadings ranging from about 0.01 to about 20 wt % onany one of the supports described below.

In general, the finishing step is carried out at finishing temperaturesof between about 200° C. to 450° C., and finishing pressures in therange of about 100 psig to 2000 psig. The finishing step may beconducted in the vapor phase or liquid phase, and may use in situgenerated H₂, external H₂, recycled H₂, or combinations thereof, asnecessary.

Other factors, such as the presence of water or undesired oxygenates,may also effect the composition and yields of the C₄₊ compounds, as wellas the activity and stability of the condensation catalyst. In suchevent, the process may include a dewatering step that removes a portionof the water prior to condensation, or a separation unit for removal ofthe undesired oxygenates. For instance, a separator unit, such as aphase separator, flash separator, extractor, purifier or distillationcolumn, may be installed prior to the condensation step so as to removea portion of the water from the reactant stream containing the volatileC₂₊O₁₋₂ oxygenates. A separation unit may also be installed to removespecific oxygenates to allow for the production of a desired productstream containing hydrocarbons within a particular carbon range, or foruse as end products or in other systems or processes.

The effectiveness of the condensation catalyst may also be influenced bythe presence of small amounts of heavier di-oxygenates andtri-oxygenates volatilized into the gas phase due to the processingconditions and their concentration in the reaction stream. Suchcompounds typically have a relative volatility (α) with respect to1-hexanol of lower than 0.03 based on pure components at 250° C., butmay be volatilized at minimal concentrations, lower pressures and highertemperatures during deconstruction reactions. They are also known tolead to coking and rapid deactivation of catalysts in condensation-typereactions. One advantage of the present invention is that such compoundsare minimized in the reaction stream and, to the extent present, theprocess conditions and catalysts employed for the condensation reactionsallows for their conversion to useable end products without significantcoking and/or deactivation of the condensation catalyst.

C₄₊ Compounds

The practice of the present invention results in the production of C₄₊alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊ cycloalkenes, aryls, fusedaryls, C₄₊ alcohols, C₄₊ ketones, C₄₊ furans and mixtures thereof. TheC₄₊ alkanes and C₄₊ alkenes have from 4 to 30 carbon atoms (C₄₋₃₀alkanes and C₄₋₃₀ alkenes) and may be branched or straight chainedalkanes or alkenes. The C₄₊ alkanes and C₄₊ alkenes may also includefractions of C₄₋₉, C₇₋₁₄, C₁₂₋₂₄ alkanes and alkenes, respectively, withthe C₄₋₉ fraction directed to gasoline, the C₇₋₁₆ fraction directed tojet fuels, and the C₁₁₋₂₄ fraction directed to diesel fuel and otherindustrial applications. Examples of various C₄₊ alkanes and C₄₊ alkenesinclude, without limitation, butane, butene, pentane, pentene,2-methylbutane, hexane, hexene, 2-methylpentane, 3-methylpentane,2,2-dimethylbutane, 2,3-dimethylbutane, heptane, heptene, octane,octene, 2,2,4,-trimethylpentane, 2,3-dimethyl hexane,2,3,4-trimethylpentane, 2,3-dimethylpentane, nonane, nonene, decane,decene, undecane, undecene, dodecane, dodecene, tridecane, tridecene,tetradecane, tetradecene, pentadecane, pentadecene, hexadecane,hexadecene, heptyldecane, heptyldecene, octyldecane, octyldecene,nonyldecane, nonyldecene, eicosane, eicosene, uneicosane, uneicosene,doeicosane, doeicosene, trieicosane, trieicosene, tetraeicosane,tetraeicosene, and isomers thereof.

The C₅₊ cycloalkanes and C₅₊ cycloalkenes have from 5 to 30 carbon atomsand may be unsubstituted, mono-substituted or multi-substituted. In thecase of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. In one embodiment, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₁₋₁₂ alkylene,a straight chain C₂₋₁₂ alkylene, a phenyl or a combination thereof. Inyet another embodiment, at least one of the substituted groups include abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, straight chain C₁₋₄ alkylene, straight chain C₂₋₄ alkylene, aphenyl or a combination thereof. Examples of desirable C₅₊ cycloalkanesand C₅₊ cycloalkenes include, without limitation, cyclopentane,cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane,methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene,ethyl-cyclohexane, ethyl-cyclohexene, propyl-cyclohexane,butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane,pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, and isomersthereof.

Aryls will generally consist of an aromatic hydrocarbon in either anunsubstituted (phenyl), mono-substituted or multi-substituted form. Inthe case of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. In one embodiment, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene,a phenyl or a combination thereof. In yet another embodiment, at leastone of the substituted groups include a branched C₃₋₄ alkyl, a straightchain C₁₋₄ alkyl, a branched C₃₋₄ alkylene, straight chain C₂₋₄alkylene, a phenyl or a combination thereof. Examples of various arylsinclude, without limitation, benzene, toluene, xylene (dimethylbenzene),ethyl benzene, para xylene, meta xylene, ortho xylene, C₉₊ aromatics,butyl benzene, pentyl benzene, hexyl benzene, heptyl benzene, oxtylbenzene, nonyl benzene, decyl benzene, undecyl benzene, and isomersthereof.

Fused aryls will generally consist of bicyclic and polycyclic aromatichydrocarbons, in either an unsubstituted, mono-substituted, ormulti-substituted form. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene,a straight chain C₂₊ alkylene, a phenyl or a combination thereof. Inanother embodiment, at least one of the substituted groups include abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, straight chain C₂₋₄ alkylene, a phenyl or a combinationthereof. Examples of various fused aryls include, without limitation,naphthalene, anthracene, tetrahydronaphthalene, anddecahydronaphthalene, indane, indene, and isomers thereof.

The C₄₊ alcohols may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ alcohols may be acompound according to the formula R¹—OH, wherein R¹ is a member selectedfrom the group consisting of a branched C₄₊ alkyl, straight chain C₄₊alkyl, a branched C₄₊ alkylene, a straight chain C₄₊ alkylene, asubstituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, asubstituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl,a phenyl and combinations thereof. Examples of desirable C₄₊ alcoholsinclude, without limitation, butanol, pentanol, hexanol, heptanol,octanol, nonanol, decanol, undecanol, dodecanol, tridecanol,tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol,nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol,tetraeicosanol, and isomers thereof.

The C₄₊ ketones may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ ketone may be acompound according to the formula

wherein R³ and R⁴ are independently a member selected from the groupconsisting of a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, abranched C₃₊ alkylene, a straight chain C₂₊ alkylene, a substituted C₅₊cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl and acombination thereof. Examples of desirable C₄₊ ketones include, withoutlimitation, butanone, pentanone, hexanone, heptanone, octanone,nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone,pentadecanone, hexadecanone, heptyldecanone, octyldecanone,nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone,tetraeicosanone, and isomers thereof.

The lighter fractions of the above, primarily C₄-C₁₂, may be separatedfor gasoline use. Moderate fractions, such as C₇-C₁₆, may be separatedfor jet fuel, while heavier fractions, i.e., C₁₁-C₂₄, may be separatedfor diesel use. The heaviest fractions may be used as lubricants orcracked to produce additional gasoline and/or diesel fractions. The C₄₊compounds may also find use as industrial chemicals, whether as anintermediate or an end product. For example, the aryls toluene, xylene,ethyl benzene, para xylene, meta xylene, ortho xylene may find use achemical intermediates for the product of plastics and other products.Meanwhile, the C₉₊ aromatics and fused aryls, such as naphthalene,anthracene, tetrahydronaphthalene, and decahydronaphthalene, may finduse as solvents in industrial processes.

Catalyst Supports

In various embodiments above, the catalyst systems include a supportsuitable for suspending the catalyst in the biomass feed stream, biomassslurry, or reactant stream. The support should be one that provides astable platform for the chosen catalyst and the reaction conditions. Thesupport may take any form which is stable at the chosen reactionconditions to function at the desired levels, and specifically stable inaqueous feedstock solutions. Such supports include, without limitation,carbon, silica, alumina, silica-alumina, acidic alumina, sulfatedalumina, phosphated alumina, zirconia, tungstate zirconia, titaniazirconia, sulfated zirconia, phosphated zirconia, titania, ceria,vanadia, nitride, boron nitride, heteropolyacids, hydroxyapatite, zincoxide, chromia, and mixtures thereof. Nanoporous supports such aszeolites, carbon nanotubes, or carbon fullerene may also be used.

One particularly preferred catalyst support is carbon, especially carbonsupports having relatively high surface areas (greater than 100 squaremeters per gram). Such carbons include activated carbon (granulated,powdered, or pelletized), activated carbon cloth, felts, or fibers,carbon nanotubes or nanohorns, carbon fullerene, high surface areacarbon honeycombs, carbon foams (reticulated carbon foams), and carbonblocks. The carbon may be produced via either chemical or steamactivation of peat, wood, lignite, coal, coconut shells, olive pits, andoil-based carbon. Another preferred support is granulated activatedcarbon produced from coconuts.

Another preferred catalyst support is zirconia. The zirconia may beproduced via precipitation of zirconium hydroxide from zirconium salts,through sol-gel processing, or any other method. The zirconia ispreferably present in a crystalline form achieved through calcination ofthe precursor material at temperatures exceeding 400° C. and may includeboth tetragonal and monoclinic crystalline phases. A modifying agent maybe added to improve the textural or catalytic properties of thezirconia. Such modifying agents include, without limitation, sulfate,tungstenate, phosphate, titania, silica, and oxides of Group IIIBmetals, especially Ce, La, or Y. In one embodiment, the deconstructioncatalyst consists of Pd:Ag on a tungstated zirconia support.

Another preferred catalyst support is titania. The titania may beproduced via precipitation from titanium salts, through sol-gelprocessing, or any other method. The titania is preferably present in acrystalline form and may include both anatase and rutile crystallinephases. A modifying agent may be added to improve the textural orcatalytic properties of the titania. Such modifying agents include,without limitation, sulfate, silica, and oxides of Group IIIB metals,especially Ce, La, or Y.

Yet another preferred catalyst support is a transitional alumina,preferentially theta alumina. The theta alumina may be produced viaprecipitation from aluminum salts, through sol-gel processing, or anyother method. Preferably, the support would be manufactured throughpeptization of a suitable aluminum hydroxide, preferentially bohemite orpseudo-bohemite, with nitric acid in the presence of an organic binder,preferentially hydroxyethyl cellulose. After forming the support mustthen be calcined to a final temperature between 900-1200° C.,preferentially greater than 1000° C. A modifying agent may be added toimprove the textural or catalytic properties of the alumina. Suchmodifying agents include, without limitation, sulfate, silica, Fe, Ce,La, Cu, Co, Mo, or W.

The support may also be treated or modified to enhance its properties.For example, the support may be treated, as by surface-modification, tomodify surface moieties, such as hydrogen and hydroxyl. Surface hydrogenand hydroxyl groups can cause local pH variations that affect catalyticefficiency. The support may also be modified, for example, by treatingit with sulfates, phosphates, tungstenates, silanes, lanthanides, alkalicompounds or alkali earth compounds. For carbon supports, the carbon maybe pretreated with steam, oxygen (from air), inorganic acids or hydrogenperoxide to provide more surface oxygen sites. The preferredpretreatment would be to use either oxygen or hydrogen peroxide. Thepretreated carbon may also be modified by the addition of oxides ofGroup IVB and Group VB. It is preferred to use oxides of W, Ti, V, Zrand mixtures thereof.

The catalyst systems, whether alone or mixed together, may be preparedusing conventional methods known to those in the art. Such methodsinclude incipient wetting, evaporative impregnation, chemical vapordeposition, wash-coating, magnetron sputtering techniques, and the like.The method chosen to fabricate the catalyst is not particularly criticalto the function of the invention, with the proviso that differentcatalysts will yield different results, depending upon considerationssuch as overall surface area, porosity, etc.

Catalyst Regeneration

During deconstruction, carbonaceous deposits build up on thedeconstruction catalyst surface through minor side reactions of thebiomass and other generated products. As these deposits accumulate,access to the catalytic sites on the surface becomes restricted and thecatalyst performance declines, resulting in lower conversion and yieldsto desired products.

To regenerate the deconstruction catalyst, the solid phase is furtherapportioned by separating the catalyst from the extractives andunreacted or under-reacted materials using a washing medium. The washingmedium can be any medium capable of washing unreacted species from thecatalyst and reactor system. Such washing medium may include any one ofseveral liquid media, such as water, alcohols, ketones, chelatingagents, acids, or other oxygenated hydrocarbons, whether alone or incombination with any of the foregoing, and which does not includematerials known to be poisons for the catalyst in use (e.g., sulfur).The washing step may include either soaking the catalyst for a period oftime (e.g., 5 or more minutes), flushing with the washing medium, or acombination of both, and at a temperature that does not cause the liquidwashing medium or the unreacted species to change to the gaseous phase.The washing step may also involve multiple flushing activities,including one or more initial washes with an organic solvent, followedby one or more washes with water, or vice-versa, until thedeconstruction catalyst is free of extractives and other unwantedmaterials. In one embodiment, the temperature is maintained below about100° C. during the washing step.

In certain applications, the deconstruction catalyst may still be in amixture with unreacted and under-reacted biomass after washing, therebyrequiring additional separation. In general, the deconstruction catalystwill tend to be more dense than the biomass and can be readily separatedusing various techniques, including cyclone separation, centrifugation,and gravitational settling, among others.

The deconstruction catalyst is then dried at a temperature and pressuresufficient to remove any water from the catalyst (e.g., 120° C. and atatmospheric pressure). Once dried, the temperature in the reactor isincreased at a rate of about 20° C. per hour to about 60° C. per hour,and is maintained at a temperature between about 300° C. and about 450°C. At temperatures between about 120° C. and about 150° C., C—O and C—Clinkages in the carbonaceous deposits are broken and CO₂ and CO arereleased from the catalyst and collected in a downstream phase separatoror removed in the gas phase. As temperatures continue to rise towardabout 450° C., C—C bond hydrogenolysis predominates. Throughout theregeneration and cooling process, a gas flow of 600-1200 ml gas/mlcatalyst per hour (GHSV) of inert gas (e.g., nitrogen) and 0.5-10%oxygen is maintained.

During the deconstruction catalyst regeneration, carbon dioxide andsmall amounts of carbon monoxide are emitted as a regeneration stream.Ultimately, the level of carbon dioxide in the regeneration streamdeclines as the regeneration progresses, providing an effective meansfor monitoring the status of the regeneration. Based on this trend, toobtain a maximum return of performance, the regeneration is continueduntil the CO₂ content of the regeneration stream is below an amountindicative of successful regeneration.

The deconstruction catalyst is considered completely regenerated whensufficient carbonaceous deposits have been removed such thatdeconstruction can be resumed. This generally occurs when the CO₂ givenoff during the regeneration decreases to an insignificant amount. In apreferred embodiment, the deconstruction catalyst is consideredregenerated when the amount of CO₂ in the regeneration stream is lessthan 4,000 ppm, more preferably less than 2,000 ppm, and most preferablyless than 1,000 ppm. To ensure that maximum regeneration is achieved,the deconstruction catalyst may need to be regenerated at its highesttemperature for a period of up to 16 hours.

The accumulation of CO₂ during regeneration can be utilized to calculatethe total grams of carbon removed per gram of catalyst. When theregeneration is run to maximize system performance, the amount of carbonper gram of catalyst can be utilized to determine average rate ofdeposit for carbonaceous species as well as provide some predictiveinformation on the duration between regenerations assuming similaroperating conditions are used.

Alternatively, reductive regeneration can be used to remove thecarbon-containing species from the catalyst surface. Reductive catalystregeneration can be accomplished by heating the catalyst in the presenceof hydrogen resulting in the production of alkanes (e.g., CH₄, C₂H₆,C₃H₈, C₄H₁₀, C₅H₁₂, C₆H₁₄, etc.). Similar to the oxidative regenerationdescribed above, measuring the amount of alkanes emitted is an effectivemeans for monitoring the regeneration status.

Extractives

In addition to lignin, cellulose and hemicellulose, biomass includesinclude ash components, such as calcium, aluminum, potassium, sodium,magnesium, chloride, sulfates, sulfites, thiols, silica, copper, iron,phosphates, and phosphorous, as well as color bodies (e.g., terpenoids,stilbenes, flavonoids), proteinaceous materials and other inorganicproducts not amenable to downstream conversion processes as thosecontemplated herein. In practicing the present invention, suchmaterials, as well as unreacted or under reacted lignin, cellulose andhemicellulose, will often be present in the product stream as a solidmaterial and removed as part of the catalytic washing process.Ultimately, the lignin, ash and other extractives can be purged from thesystem and used in other processes. For example, the lignin can beburned to provide process heat, while the proteinaceous material can beused for animal feed or as other products. The unreacted orunder-reacted cellulose and hemicellulose can be recycled to the biomassfeed stream and processed until fully reacted.

Liquid Fuels and Chemicals

The C₄₊ compounds derived from the practice of the present invention asdescribed above can be fractionated and used in liquid fuels, such asgasoline, jet fuel (kerosene) or diesel fuel. The C₄₊ compounds can alsobe fractionated and used in chemical processes, such as those common tothe petro-chemical industry. For example, the product stream from thepresent invention can be fractionated to collect xylenes for use in theproduction of phthalic acid, polyethylene terephthalate (PET), andultimately renewable plastics or solvents. Benzene can also be collectedand processed for the production of renewable polystyrenes,polycarbonates, polyurethane, epoxy resins, phenolic resins, and nylon.Toluene can be collected and processed for the production of toluenediisocyanate, and ultimately renewable solvents, polyurethane foam orTNT, among others.

In one embodiment, the C₄₊ compounds derived from the practice of thepresent invention are separated into various distillation fractions byany means known for liquid fuel compositions. In such applications, theproduct stream having at least one C₄₊ compound derived from the processas described above is preferably separated into more than onedistillation fraction, wherein at least one of the distillationfractions is a lighter, moderate or heavier fraction. The lighterfractions, primarily C₄-C₉, i.e., C₄, C₅, C₆, C₇, C₈, and C₉, may beseparated for gasoline use. The moderate fractions, primarily C₇-C₁₄,i.e., C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, and C₁₄, may be separated for useas kerosene, e.g., for jet fuel use. Heavier fractions, primarilyC₁₂-C₂₄, i.e., C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂,C₂₃, and C₂₄, may be separated for diesel fuel use. The heaviestfractions, C₂₅₊ and C₃₀₊, i.e., C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, C₃₀, C₃₁, C₃₂,C₃₃, C₃₄, C₃₅, etc., may be used as lubricants, fuel oils, or may becracked to produce additional fractions for use in gasoline, keroseneand/or diesel fractions.

Because the C₄₊ compounds are derived from biomass, the age of thecompounds, or fractions containing the compounds, is less than 100 yearsold, preferably less than 40 years old, more preferably less than 20years old, as calculated from the carbon 14 concentration of thecomponent.

The lighter fractions having at least one biomass-derived C₄₊ compoundshas one or more of the following properties (LF-i to LF-vi):

-   -   (LF-i) a final boiling point in the range of from 150 to 220°        C., more preferably in the range of from 160 to 210° C.;    -   (LF-ii) a density at 15° C. in the range of from 700 to 890        kg/m³, more preferably in the range of from 720 to 800 kg/m³;    -   (LF-iii) a sulfur content of at most 5 mg/kg, more preferably at        most 1 mg/kg;    -   (LF-iv) an oxygen content of at most 3.5% wt., more preferably        at most 3.0% wt., typically at most 2.7% wt., and more typically        at most 0.5%;    -   (LF-v) a RON in the range of from 80 to 110, more preferably in        the range of from 90 to 100;    -   (LF-vi) a MON in the range of from 70 to 100, more preferably in        the range of from 80 to 90.

In such instance, the lighter fraction has properties which accord eachof the properties detailed in LF-i to LF-vi above, more convenientlywith each of the preferred values for each of the properties detailed inLF-i to LF-vi above.

The moderate fractions having at least one biomass-derived C₄₊ compoundhas one or more of the following properties (MF-i to MF-vix):

-   -   (MF-i) an initial boiling point in the range of from 120 to 215°        C., more preferably in the range of from 130 to 205° C.;    -   (MF-ii) a final boiling point in the range of from 220 to 320°        C., more preferably in the range of from 230 to 300° C.;    -   (MF-iii) a density at 15° C. in the range of from 700 to 890        kg/m³, more preferably in the range of from 730 to 840 kg/m³;    -   (MF-iv) a sulfur content of at most 0.1% wt., more preferably at        most 0.01% wt.;    -   (MF-v) a total aromatics content of at most 30% vol., more        preferably at most 25% vol., even more preferably at most 20%        vol., most preferably at most 15% vol.;    -   (MF-vi) a freeze point of −40° C. or lower, more preferably at        least −47° C. or lower;    -   (MF-vii) a smoke point of at least 18 mm, more preferably at        least 19 mm, even more preferably at least 25 mm;    -   (MF-viii) a viscosity at −20° C. in the range of from 1 to 10        cSt, more preferably in the range of from 2 to 8 cSt.;    -   (MF-vix) a specific energy content in the range of from 40 to 47        MJ/kg, more preferably in the range of from 42 to 46 MJ/kg.

In such instance, the moderate fraction has properties which accord eachof the properties detailed in MF-i to MF-vix above, more convenientlywith each of the preferred values for each of the properties detailed inMF-i to MF-vix above.

The heavier fraction having at least one biomass-derived C₄₊ compoundhas one or more of the following properties (HF-i to HF-vi):

-   -   (HF-i) a T95 in the range of from 220 to 380° C., more        preferably in the range of from 260 to 360° C.;    -   (HF-ii) a flash point in the range of from 30 to 70° C., more        preferably in the range of from 33 to 60° C.;    -   (HF-iii) a density at 15° C. in the range of from 700 to 900        kg/m³, more preferably in the range of from 750 to 850 kg/m³;    -   (HF-iv) a sulfur content of at most 5 mg/kg, more preferably at        most 1 mg/kg;    -   (HF-v) an oxygen content of at most 10% wt., more preferably at        most 8% wt.;    -   (HF-vi) a viscosity at 40° C. in the range of from 0.5 to 6 cSt,        more preferably in the range of from 1 to 5 cSt.

In this instance, the heavier fraction has properties which accord eachof the properties detailed in HF-i to HF-vi above, more convenientlywith each of the preferred values for each of the properties detailed inHF-i to HF-vi above.

In liquid fuels applications, the fraction may be used as a neat fuelproduct or used as a biomass-derived blending component for a finalliquid fuel composition. Accordingly, the present invention includes aliquid fuel composition containing one or more of the lighter fractions,moderate fractions or heavy fractions described above, as abiomass-derived blending component.

The volume of the biomass-derived blending component in the liquid fuelcomposition should be at least 0.1% vol., based on the overall volume ofthe liquid fuel composition. For example, the amount of thebiomass-derived blending component present in the liquid fuelcomposition should accord with one or more of the parameters (i) to (xx)listed below:

(i) at least 0.5% vol.

(ii) at least 1% vol

(iii) at least 1.5% vol

(iv) at least 2% vol

(v) at least 2.5% vol

(vi) at least 3% vol

(vii) at least 3.5% vol

(viii) at least 4% vol

(ix) at least 4.5% vol

(x) at least 5% vol

(xi) at most 99.5% vol.

(xii) at most 99% vol.

(xiii) at most 98% vol.

(xiv) at most 97% vol.

(xv) at most 96% vol.

(xvi) at most 95% vol.

(xvii) at most 90% vol.

(xviii) at most 85% vol.

(xix) at most 80% vol.

(xx) at most 75% vol.

The amount of the biomass-derived blending component present in theliquid fuel composition of the present invention accords with oneparameter selected from (i) to (x) above, and one parameter selectedfrom (xi) to (xx) above.

For gasoline compositions according to the present invention, the amountof the biomass-derived blending component present in the gasolinecomposition will be in the range of from 0.1 to 60% vol, 0.5 to 55% volor 1 to 50% vol.

For diesel fuel compositions according to the present invention, theamount of the biomass-derived blending component present in the dieselfuel composition will be in the range of from 0.1 to 60% vol, 0.5 to 55%vol or 1 to 50% vol.

For kerosene compositions according to the present invention, the amountof the biomass-derived blending component present in the kerosenecomposition will be in the range of from 0.1 to 90% vol, 0.5 to 85% volor 1 to 80% vol, such as in the range of from 0.1 to 60% vol, 0.5 to 55%vol or 1 to 50% vol.

The liquid fuel composition of the present invention is typicallyselected from a gasoline, kerosene or diesel fuel composition. If theliquid fuel composition is a gasoline composition, then the gasolinecomposition has an initial boiling point in the range of from 15° C. to70° C. (IP123), a final boiling point of at most 230° C. (IP123), a RONin the range of from 85 to 110 (ASTM D2699) and a MON in the range offrom 75 to 100 (ASTM D2700).

If the liquid fuel composition is a kerosene composition, then thekerosene composition has an initial boiling point in the range of from110 to 180° C., a final boiling point in the range of from 200 to 320°C. and a viscosity at −20° C. in the range of from 0.8 to 10 mm²/s (ASTMD445).

If the liquid fuel composition is a diesel fuel composition, then thediesel fuel composition has an initial boiling point in the range offrom 130° C. to 230° C. (IP123), a final boiling point of at most 410°C. (IP123) and a cetane number in the range of from 35 to 120 (ASTMD613).

Preferably, the liquid fuel composition of the present inventionadditionally comprises one or more fuel additive.

Gasoline Compositions

The gasoline composition according to the present invention typicallycomprises mixtures of hydrocarbons boiling in the range from 15 to 230°C., more typically in the range of from 25 to 230° C. (EN-ISO 3405). Theinitial boiling point of the gasoline compositions according to thepresent invention are in the range of from 15 to 70° C. (IP123),preferably in the range of from 20 to 60° C., more preferably in therange of from 25 to 50° C. The final boiling point of the gasolinecompositions according to the present invention is at most 230° C.,preferably at most 220° C., more preferably at most 210° C. The optimalranges and distillation curves typically varying according to climateand season of the year.

In addition to the biomass-derived blending component, the hydrocarbonsin the gasoline composition may be derived by any means known in theart, conveniently the hydrocarbons may be derived in any known mannerfrom straight-run gasoline, synthetically-produced aromatic hydrocarbonmixtures, thermally or catalytically cracked hydrocarbons, hydro-crackedpetroleum fractions, catalytically reformed hydrocarbons or mixtures ofthese.

The research octane number (RON) of the gasoline compositions accordingto the present invention is in the range of from 85 to 110 (ASTM D2699).Preferably, the RON of the gasoline composition will be at least 90, forinstance in the range of from 90 to 110, more preferably at least 91,for instance in the range of from 91 to 105, even more preferably atleast 92, for instance in the range of from 92 to 103, even morepreferably at least 93, for instance in the range of from 93 to 102, andmost preferably at least 94, for instance in the range of from 94 to100.

The motor octane number (MON) of the gasoline compositions according tothe present invention is in the range of from 75 to 100 (ASTM D2699).Preferably, the MON of the gasoline composition will be at least 80, forinstance in the range of from 80 to 100, more preferably at least 81,for instance in the range of from 81 to 95, even more preferably atleast 82, for instance in the range of from 82 to 93, even morepreferably at least 83, for instance in the range of from 83 to 92, andmost preferably at least 84, for instance in the range of from 84 to 90.

Typically, gasoline compositions comprise a mixture of componentsselected from one or more of the following groups: saturatedhydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, andoxygenated hydrocarbons. Conveniently, the gasoline composition maycomprise a mixture of saturated hydrocarbons, olefinic hydrocarbons,aromatic hydrocarbons, and, optionally, oxygenated hydrocarbons.

Typically, the olefinic hydrocarbon content of the gasoline compositionis in the range of from 0 to 40% by volume based on the gasoline (ASTMD1319); preferably, the olefinic hydrocarbon content of the gasolinecomposition is in the range of from 0 to 30% by volume based on thegasoline composition, more preferably, the olefinic hydrocarbon contentof the gasoline composition is in the range of from 0 to 20% by volumebased on the gasoline composition.

Typically, the aromatic hydrocarbon content of the gasoline compositionis in the range of from 0 to 70% by volume based on the gasoline (ASTMD1319), for instance the aromatic hydrocarbon content of the gasolinecomposition is in the range of from 10 to 60% by volume based on thegasoline composition; preferably, the aromatic hydrocarbon content ofthe gasoline composition is in the range of from 0 to 50% by volumebased on the gasoline composition, for instance the aromatic hydrocarboncontent of the gasoline composition is in the range of from 10 to 50% byvolume based on the gasoline composition.

The benzene content of the gasoline composition is at most 10% byvolume, more preferably at most 5% by volume, especially at most 1% byvolume based on the gasoline composition.

The gasoline composition preferably has a low or ultra-low sulfurcontent, for instance at most 1000 ppmw (parts per million by weight),preferably no more than 500 ppmw, more preferably no more than 100, evenmore preferably no more than 50 and most preferably no more than even 10ppmw.

The gasoline composition also preferably has a low total lead content,such as at most 0.005 g/l, most preferably being lead free—having nolead compounds added thereto (i.e. unleaded).

When the gasoline composition comprises oxygenated hydrocarbons, atleast a portion of non-oxygenated hydrocarbons will be substituted foroxygenated hydrocarbons. The oxygen content of the gasoline may be up to30% by weight (EN 1601) based on the gasoline composition. For example,the oxygen content of the gasoline may be up to 25% by weight,preferably up to 10% by weight. Conveniently, the oxygenateconcentration will have a minimum concentration selected from any one of0, 0.2, 0.4, 0.6, 0.8, 1.0, and 1.2% by weight, and a maximumconcentration selected from any one of 5, 4.5, 4.0, 3.5, 3.0, and 2.7%by weight.

Examples of oxygenated hydrocarbons that may be incorporated into thegasoline, other than the oxygenated hydrocarbons that may be present inthe biomass-derived blending component, include alcohols, ethers,esters, ketones, aldehydes, carboxylic acids and their derivatives, andoxygen containing heterocyclic compounds. Preferably, the oxygenatedhydrocarbons incorporated are selected from alcohols (such as methanol,ethanol, propanol, iso-propanol, butanol, tert-butanol and iso-butanol),ethers (preferably ethers containing 5 or more carbon atoms permolecule, e.g., methyl tert-butyl ether) and esters (preferably esterscontaining 5 or more carbon atoms per molecule); a particularlypreferred oxygenated hydrocarbon is ethanol derived from biomass.

When oxygenated hydrocarbons are present in the gasoline composition,the amount of oxygenated hydrocarbons in the gasoline composition mayvary over a wide range. For example, gasolines comprising a majorproportion of oxygenated hydrocarbons are currently commerciallyavailable in countries such as Brazil and U.S.A, e.g., E85, as well asgasoline comprising a minor proportion of oxygenated hydrocarbons, e.g.,E10 and E5. Therefore, the amount of oxygenated hydrocarbons present inthe gasoline composition is preferably selected from one of thefollowing amounts: up to 85% by volume; up to 65% by volume; up to 30%by volume; up to 20% by volume; up to 15% by volume; and up to 10% byvolume, depending upon the desired final formulation of the gasoline.Conveniently, the gasoline composition may contain at least 0.5, 1.0 or2.0% by volume oxygenated hydrocarbons.

Examples of suitable gasoline compositions include gasolines having anolefinic hydrocarbon content of from 0 to 20% by volume (ASTM D1319), anoxygen content of from 0 to 5% by weight (EN 1601), an aromatichydrocarbon content of from 0 to 50% by volume (ASTM D1319) and abenzene content of at most 1% by volume.

While not critical to the present invention, the gasoline compositionsof the present invention may conveniently additionally include one ormore fuel additive. The concentration and nature of the fuel additive(s)that may be included in the gasoline composition of the presentinvention is not critical. Non-limiting examples of suitable types offuel additives that can be included in the gasoline composition of thepresent invention include anti-oxidants, corrosion inhibitors,detergents, dehazers, antiknock additives, metal deactivators,valve-seat recession protectant compounds, dyes, friction modifiers,carrier fluids, diluents and markers. Examples of suitable suchadditives are described generally in U.S. Pat. No. 5,855,629.

The fuel additives can also be blended with one or more diluents orcarrier fluids, to form an additive concentrate, the additiveconcentrate can then be admixed with the gasoline composition of thepresent invention. The (active matter) concentration of any additivespresent in the gasoline composition of the present invention ispreferably up to 1 percent by weight, more preferably in the range from5 to 1000 ppmw, advantageously in the range of from 75 to 300 ppmw, suchas from 95 to 150 ppmw.

Alternatively, the gasoline composition of the present invention may bean aviation gasoline. If the gasoline composition is an aviationgasoline then, depending upon the grade of the aviation gasoline, theLean Mixture Motor Octane Number will be at least 80 (ASTM D2700) andthe Rich Mixture Octane Number will be at least 87 (ASTM D 909), or theLean Mixture Motor Octane Number will be at least 99.5 (ASTM D2700) andthe Performance Number will be at least 130 (ASTM D 909). Furthermore,if the gasoline composition is an aviation gasoline then the Reid VapourPressure at 37.8° C. will be in the range of from 38.0 to 49.0 kPa (ASTMD323), the final boiling point will be at most 170° C. (ASTM D 86), andthe tetraethyl lead content will be at most 0.85 gPb/1.

Kerosene Fuel Compositions

The kerosene fuel compositions of the present invention have use inaviation engines, such as jet engines or aero diesel engines, but alsoin any other suitable power or lighting source. In addition to thebiomass-derived blending component, the kerosene fuel composition maycomprise a mixture of two or more different fuel components, and/or beadditivated as described below.

The kerosene fuel compositions will typically have boiling points withinthe range of 80 to 320° C., preferably in the range of 110 to 320° C.,more preferably in the range of from 130 to 300° C., depending on gradeand use. They will typically have a density from 775 to 845 kg/m³,preferably from 780 to 830 kg/m³, at 15° C. (e.g., ASTM D4502 or IP365). They will typically have an initial boiling point in the range 80to 150° C., preferably in the range 110 to 150° C., and a final boilingpoint in the range 200 to 320° C. Their kinematic viscosity at −20° C.(ASTM D445) is typically in the range of from 0.8 to 10 mm²/s,preferably from 1.2 to 8.0 mm²/s.

The kerosene fuel composition of the present invention preferablycontains no more than 3000 ppmw sulfur, more preferably no more than2000 ppmw, or no more than 1000 ppmw, or no more than 500 ppmw sulfur.

The kerosene fuel composition or the components thereof may beadditivated (additive-containing) or unadditivated (additive-free). Ifadditivated, e.g., at the refinery or in later stages of fueldistribution, it will contain minor amounts of one or more additivesselected for example from anti-static agents (e.g., STADIS™ 450 (ex.Octel)), antioxidants (e.g., substituted tertiary butyl phenols), metaldeactivator additives (e.g., N,N′-disalicylidene 1,2-propanediamine),fuel system icing inhibitor additives (e.g., diethylene glycolmonomethyl ether), corrosion inhibitor/lubricity improver additives(e.g., APOLLO™ PR119 (ex. Apollo), DCI 4A (ex. Octel), NALCO™ 5403 (ex.Nalco)), or thermal stability improving additives (e.g., APA 101™, (ex.Shell)) that are approved in international civil and/or military jetfuel specifications.

The kerosene fuel composition of the present invention is particularlyapplicable where the kerosene fuel composition is used or intended to beused in a jet engine. Unless otherwise stated, the (active matter)concentration of each such additional component in the additivatedkerosene fuel composition is at levels required or allowed ininternational jet fuel specifications. In the above, amounts(concentrations, % v, ppmw, wt %) of components are of active matter,i.e. exclusive of volatile solvents/diluent materials, unless otherwisestipulated in the relevant specification.

Diesel Fuel Compositions

The diesel fuel composition according to the present invention typicallyincludes mixtures of hydrocarbons boiling in the range from 130 to 410°C., more typically in the range of from 150 to 400° C. The initialboiling point of the diesel fuel compositions according to the presentinvention are in the range of from 130 to 230° C. (IP123), preferably inthe range of from 140 to 220° C., more preferably in the range of from150 to 210° C. The final boiling point of the diesel fuel compositionsaccording to the present invention is at most 410° C., preferably atmost 405° C., more preferably at most 400° C.

In addition to the biomass-derived blending component, the diesel fuelcomposition may comprise a mixture of two or more different diesel fuelcomponents, and/or be additivated as described below.

Such diesel fuel compositions will contain one or more base fuels whichmay typically comprise liquid hydrocarbon middle distillate gas oil(s),for instance petroleum derived gas oils. Such fuels will typically haveboiling points within the range described above, depending on grade anduse. They will typically have a density from 750 to 1000 kg/m³,preferably from 780 to 860 kg/m³, at 15° C. (e.g., ASTM D4502 or IP 365)and a cetane number (ASTM D613) of from 35 to 120, more preferably from40 to 85. They will typically have an initial boiling point in the rangedescribed above and a final boiling point of at most 410° C., preferablyat most 405° C., more preferably at most 400° C., most preferably in therange 290 to 400° C. Their kinematic viscosity at 40° C. (ASTM D445)might suitably be from 1.2 to 4.5 mm²/s.

An example of a petroleum derived gas oil is a Swedish Class 1 basefuel, which will have a density from 800 to 820 kg/m³ at 15° C. (SS-ENISO 3675, SS-EN ISO 12185), a T95 of 320° C. or less (SS-EN ISO 3405)and a kinematic viscosity at 40° C. (SS-EN ISO 3104) from 1.4 to 4.0mm²/s, as defined by the Swedish national specification EC1.

Optionally, non-mineral oil based fuels, such as biofuels (other thanthe component having at least one C₄₊ compound derivable from awater-soluble oxygenated hydrocarbon) or Fischer-Tropsch derived fuels,may also form or be present in the diesel fuel. Such Fischer-Tropschfuels may for example be derived from natural gas, natural gas liquids,petroleum or shale oil, petroleum or shale oil processing residues, coalor biomass.

The diesel fuel composition preferably contains no more than 5000 ppmwsulfur, more preferably no more than 500 ppmw, or no more than 350 ppmw,or no more than 150 ppmw, or no more than 100 ppmw, or no more than 70ppmw, or no more than 50 ppmw, or no more than 30 ppmw, or no more than20 ppmw, or most preferably no more than 15 ppmw sulfur.

The diesel base fuel may itself be additivated (additive-containing) orunadditivated (additive-free). If additivated, e.g., at the refinery, itwill contain minor amounts of one or more additives selected for examplefrom anti-static agents, pipeline drag reducers, flow improvers (e.g.,ethylene/vinyl acetate copolymers or acrylate/maleic anhydridecopolymers), lubricity additives, antioxidants and wax anti-settlingagents.

The diesel fuel typically also includes one or more fuel additive.Detergent-containing diesel fuel additives are known and commerciallyavailable. Such additives may be added to diesel fuels at levelsintended to reduce, remove, or slow the build-up of engine deposits.Examples of detergents suitable for use in diesel fuel additives for thepresent purpose include polyolefin substituted succinimides orsuccinamides of polyamines, for instance polyisobutylene succinimides orpolyisobutylene amine succinamides, aliphatic amines, Mannich bases oramines and polyolefin (e.g., polyisobutylene) maleic anhydrides.Succinimide dispersant additives are described for example inGB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 andWO-A-98/42808. Particularly preferred are polyolefin substitutedsuccinimides such as polyisobutylene succinimides.

The diesel fuel additive mixture may contain other components inaddition to the detergent. Examples are lubricity enhancers; dehazers(e.g., alkoxylated phenol formaldehyde polymers); anti-foaming agents(e.g., polyether-modified polysiloxanes); ignition improvers (cetaneimprovers) (e.g., 2-ethylhexyl nitrate (EHN), cyclohexyl nitrate,di-tert-butyl peroxide and those disclosed in U.S. Pat. No. 4,208,190 atcolumn 2, line 27 to column 3, line 21); anti-rust agents (e.g., apropane-1,2-diol semi-ester of tetrapropenyl succinic acid, orpolyhydric alcohol esters of a succinic acid derivative, the succinicacid derivative having on at least one of its alpha-carbon atoms anunsubstituted or substituted aliphatic hydrocarbon group containing from20 to 500 carbon atoms (e.g., the pentaerythritol diester ofpolyisobutylene-substituted succinic acid)); corrosion inhibitors;reodorants; anti-wear additives; anti-oxidants (e.g., phenolics such as2,6-di-tert-butylphenol, or phenylenediamines such asN,N′-di-sec-butyl-p-phenylenediamine); metal deactivators; combustionimprovers; static dissipator additives; cold flow improvers; and waxanti-settling agents.

The diesel fuel additive mixture may contain a lubricity enhancer,especially when the diesel fuel composition has a low sulfur content(e.g., 500 ppmw or less). In the additivated diesel fuel composition,the lubricity enhancer is conveniently present at a concentration ofless than 1000 ppmw, preferably between 50 and 1000 ppmw, morepreferably between 70 and 1000 ppmw. Suitable commercially availablelubricity enhancers include ester- and acid-based additives. Otherlubricity enhancers are described in the patent literature, inparticular in connection with their use in low sulfur content dieselfuels, for example in: The paper by Danping Wei and H. A. Spikes, “TheLubricity of Diesel Fuels”, Wear, III (1986) 217-235; WO-A-95/33805(describing cold flow improvers to enhance lubricity of low sulfurfuels); WO-A-94/17160 (describing certain esters of a carboxylic acidand an alcohol wherein the acid has from 2 to 50 carbon atoms and thealcohol has 1 or more carbon atoms, particularly glycerol monooleate anddi-isodecyl adipate, as fuel additives for wear reduction in a dieselengine injection system); U.S. Pat. No. 5,490,864 (describing certaindithiophosphoric diester-dialcohols as anti-wear lubricity additives forlow sulfur diesel fuels); and WO-A-98/01516 (describing certain alkylaromatic compounds having at least one carboxyl group attached to theiraromatic nuclei, to confer anti-wear lubricity effects particularly inlow sulfur diesel fuels).

It may also be preferred for the diesel fuel composition to contain ananti-foaming agent, more preferably in combination with an anti-rustagent and/or a corrosion inhibitor and/or a lubricity enhancingadditive.

Unless otherwise stated, the (active matter) concentration of each suchadditive component in the additivated diesel fuel composition ispreferably up to 10000 ppmw, more preferably in the range from 0.1 to1000 ppmw, advantageously from 0.1 to 300 ppmw, such as from 0.1 to 150ppmw.

The (active matter) concentration of any dehazer in the diesel fuelcomposition will preferably be in the range from 0.1 to 20 ppmw, morepreferably from 1 to 15 ppmw, still more preferably from 1 to 10 ppmw,advantageously from 1 to 5 ppmw. The (active matter) concentration ofany ignition improver present will preferably be 2600 ppmw or less, morepreferably 2000 ppmw or less, conveniently from 300 to 1500 ppmw. The(active matter) concentration of any detergent in the diesel fuelcomposition will preferably be in the range from 5 to 1500 ppmw, morepreferably from 10 to 750 ppmw, most preferably from 20 to 500 ppmw.

In the case of a diesel fuel composition, for example, the fuel additivemixture will typically contain a detergent, optionally together withother components as described above, and a diesel fuel-compatiblediluent, which may be a mineral oil, a solvent such as those sold byShell companies under the trade mark “SHELLSOL”, a polar solvent such asan ester and, in particular, an alcohol, e.g., hexanol, 2-ethylhexanol,decanol, isotridecanol and alcohol mixtures such as those sold by Shellcompanies under the trade mark “LINEVOL”, especially LINEVOL 79 alcoholwhich is a mixture of C₇₋₉ primary alcohols, or a C₁₂₋₁₄ alcohol mixturewhich is commercially available.

The total content of the additives in the diesel fuel composition may besuitably between 0 and 10000 ppmw and preferably below 5000 ppmw. In theabove, amounts (concentrations, % vol, ppmw, % wt) of components are ofactive matter, i.e. exclusive of volatile solvents/diluent materials.

The following examples are to be considered illustrative of variousaspects of the invention and should not be construed to limit the scopeof the invention, which are defined by the appended claims.

EXAMPLES Example 1

Product streams from the examples described below were analyzed asfollows. The organic liquid phase was collected and analyzed usingeither gas chromatograph with mass spectrometry detection or flameionization detection. Component separation was achieved using a columnwith a bonded 100% dimethyl polysiloxane stationary phase. Relativeconcentrations of individual components were estimated via peakintegration and dividing by the sum of the peak areas for an entirechromatogram. Compounds were identified by comparison to standardretention times and/or comparison of mass spectra to a compiled massspectral database. Vapor phase compositions, for the non-condensablespecies, were determined by gas chromatography with a thermalconductivity detector and flame ionization or gas chromatography with aflame ionization detector or mass spectrometry detectors for other vaporphase components (e.g., aqueous or organic phase condensable species).The liquid phase fraction was analyzed by gas chromatography with andwithout a derivatization of the organic components of the fraction usinga flame ionization detector. Product yields are represented by the feedcarbon present in each product fraction. The weight hourly spacevelocity (WHSV) was defined as the weight of feed introduced into thesystem per weight of catalyst per hour, and based on the weight of theoxygenated hydrocarbon feed only, excluding water present in the feed.

Example 2

A biomass feed stream containing 10% (w/v) microcrystalline cellulose(MCC) in water was converted to a gas phase containing volatile C₂₊O₁₋₂oxygenates and a liquid phase using modified palladium ontungstated-zirconia oxide support. The conversion was carried out in a300 ml Parr reactor at 260° C. and 1000 psi H₂, with a 15 minutereaction time. The reaction included a catalyst:biomass ratio of 1:3.

Hydrogen sparging and constant mixing at 800 rpm was used to increasemixing and catalyst contact. Mixing occurred from the start of heatingto the end of cooling. The constant sparging allowed volatile C₂₊O₁₋₂oxygenates to be collected overhead and separated from the residualaqueous products left in the reactor. Both liquid phase and vapor phaseproducts can be seen in FIGS. 3, 4 a, 4 b, and 5. FIG. 3, in particular,provides the overall conversion and selectivity. The condensed vaporstream contained C₂₊O₁₋₂ oxygenates as shown in FIG. 6 and in Table 1below. Non-condensable gas products from the vapor stream were analyzedand can be seen in FIG. 7.

TABLE 1 Organic Product Distribution of MCC Species % 1-HEXANOL 10.61-Octanol 2.6 CYCLOPENTANONE, 2-METHYL- 2.4 1-NONANOL 2.3 1-DECANOL 2.01-Pentanol 1.6 2-Nonanone 1.5 (6Z)-Nonen-1-ol 1.5 1-HEPTANOL 1.4Cyclopentanemethanol 1.2 3-Cyclopentyl-1-propanol 1.2 1-Dodecanol 1.2Phenol, 2,3-dimethyl- 1.0 2-Hexanone 1.0

Through the use of sparging and vapor phase sampling the condensedvolatile oxygenates consisted primarily of alcohols and othermono-oxygenates, leaving sugars and polyols in the liquid phase. As seenby the organic product breakdown in Table 1 and FIG. 6, the organicstream collected with the vapor phase is primarily alcohols and ketoneswith some unidentified compounds. Carbon losses through thenon-condensable gas stream are minimal as noted by the gas productanalysis (FIG. 7) showing almost no carbon dioxide or monoxide.

Example 3

A biomass feed stream containing 12-17% (w/v) loblolly pine in water wasconverted to a gas phase containing volatile C₂₊O₁₋₂ oxygenates and aliquid phase using modified palladium on a tungstated-zirconia oxidesupport. The conversion was carried out in a 300 ml Parr reactor at 280°C. and 1000 psi H₂, with a 15 minute reaction time. The reactionincluded a catalyst:biomass ratio of 1:3.

Hydrogen sparging and constant mixing at 800 rpm was used to increasemixing and catalyst contact. Mixing occurred from the start of heatingto the end of cooling. The constant sparging allowed volatile C₂₊O₁₋₂oxygenates to be collected overhead and separated from the residualliquid phase products left in the reactor. The volatile oxygenatescollected were then condensed and analyzed. Less volatile residualliquid phase products were collected after the reactor was cooled andsimilarly analyzed.

The results of the analysis of both the vapor phase and liquid phaseproducts are provided in FIGS. 8, 9 a, 9 b, and 10. FIG. 11 is ananalysis of the non-condesnable vapor phase products. The vapor phasecontained volatile C₂₊O₁₋₂ oxygenates (both mono- and di-oxygenatedhydrocarbons), while the liquid phase portion consisted primarily ofsugars. Minimal carbon losses through the non-condensable gas productwere observed with minor carbon monoxide and carbon dioxide levels inthe analysis.

Example 4

FIG. 12 shows a process diagram illustrating an exemplary reactor systemthat is useful in practicing the condensation reaction of the presentinvention. Volatile oxygenates, such as C₂₊O₁₋₂ alcohols, ketones,cyclic ethers, organic acids, or other poly-oxygenated compounds, enterthe system in stream 202 and are directed through the condensationreactor (in this case a dehydration/oligomerization reactor). Hydrogen(whether external, recycled, in situ H₂, or a combination thereof) isco-fed to the reactor in stream 301.

The product stream from the condensation reactor is sent to the lightsremoval column, where moderate and heavy hydrocarbons (e.g, kerosene,diesel fuel, and lubricants) are separated in the bottoms to providestream 411. The lighter components in the overhead are sent to a threephase separator. A gas phase stream of predominantly hydrogen and carbondioxide, with lower amounts of light hydrocarbons, is removed in stream404. The liquid phase, composed of water and low levels of organiccompounds, is removed in stream 412. A three phase separator could alsobe used to remove the liquid phase upstream of the column. The overheadorganic phase is split into three streams; (1) reflux back into thecolumn, stream 406, (2) net product, stream 407, (3) recycle back to thereactor system, stream 408. In certain embodiments, the recycle streamcan be sent back to the condensation reactor. Alkenes and residualoxygenates can be further oligomerized to C₃-C₃₀ hydrocarbons (e.g., C₃,C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈,C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, and C₃₀.

Example 5

A condensation catalyst was prepared by dissolving nickel nitrate inwater and then adding the mixture to an alumina bound ZSM-5 zeolitepreparation (SiO₂:Al₂O₃ 30:1, ⅛″ extrudates) using an incipient wetnesstechnique to target a nickel loading of 1.0 weight %. The preparationwas dried overnight (e.g., more than 4 hours, or 5 hours, or 6 hours, or7 hours, or 8 hours, and less than 16 hours, or 15 hours, or 14 hours,or 13 hours, or 12 hours, or 11 hours, or hours) in a vacuum oven andsubsequently calcined in a stream of flowing air at 400° C.

Example 6

A condensation catalyst was prepared by dissolving copper nitrate inwater and then adding the mixture to a tungstated zirconia catalystsupport (N or Pro Saint-Gobain, Product code SZ31164, with particlesizes restricted to those that were maintained on a 60 mesh screen afterpassing through an 18 mesh screen) using an incipient wetness techniqueto target a copper loading of 10% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight (e.g., more than 4 hours, or 5 hours, or 6 hours, or 7 hours,or 8 hours, and less than 16 hours, or 15 hours, or 14 hours, or 13hours, or 12 hours, or 11 hours, or hours) in a vacuum oven at 100° C.and subsequently calcined in a stream of flowing air at 400° C.

Example 7

A condensation catalyst was prepared by dissolving palladium nitrate andsilver nitrate in water and then adding the mixture to a tungstatedzirconia catalyst support (N or Pro Saint-Gobain, Product code SZ31164,with particle sizes restricted to those that were maintained on a 60mesh screen after passing through an 18 mesh screen) using an incipientwetness technique to target a palladium loading of 0.5% and a silverloading of 0.5% on the catalyst after subsequent decomposition of themetal precursors. The preparation was dried overnight (e.g., more than 4hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours, and less than 16hours, or 15 hours, or 14 hours, or 13 hours, or 12 hours, or 11 hours,or 10 hours) in a vacuum oven at 100° C. and subsequently calcined in astream of flowing air at 400° C.

Example 8

A stream of volatile C₂₊O₁₋₂ oxygenates similar in composition to thatproduced in Example 2 and illustrated by FIG. 6 was converted to aproduct stream of C₄₊ hydrocarbons using the condensation catalystsdescribed in Examples 5 and 6. The composition of the intermediatestream being fed into the condensation reactor is described in Table 2,with 99% of all components having carbon chain lengths of six or less.

TABLE 2 Composition of Organic Phase Intermediate Stream Breakdown ofOrganic Phase Composition Alkanes % of carbon in organic phase 15.0Total Mono-oxygenates % of carbon in organic phase 75.7 Alcohols % ofcarbon in organic phase 40.1 Ketones % of carbon in organic phase 11.4Cyclic Ethers % of carbon in organic phase 19.3 Cyclic Mono-oxygenates %of carbon in organic phase 5.0 Organic Acids % of carbon in organicphase 6.9 C6− Components % of carbon in organic phase 99.0

The stream of volatile oxygenates was fed over the condensation catalystusing the process configuration described in Example 4. The catalyst wasloaded as a packed bed with 12″ height in a 1″ diameter shell and tubereactor. Reaction conditions are described in Table 3.

The heavy liquid stream (411 in FIG. 12) was collected and analyzedusing the techniques listed in Example 1. Table 3 shows the organicproduct yields and composition as a function of catalyst formulation.Non-condensed components are those components that do not require theformation of new carbon-carbon bonds to be produced from the given feed.For simplicity, all compounds containing six or fewer carbon atoms areconsidered to be non-condensed components (e.g., C₁, C₂, C₃, C₄, C₅,C₆). Total condensation products are those compounds containing seven ormore carbon atoms (e.g., C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆,C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂, C₂₃, C₂₄, C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, andC₃₀), which require the formation of new carbon-carbon bonds to beformed from the given feedstock.

The exception to this is the “di-oxygenate” category, which are estersthat lack a continuous carbon backbone. These compounds would not retaintheir chain lengths if hydrogenated to a finished liquid fuel.

The “Unclassified” category contains compounds that are too heavy for anaccurate identification from the analysis technique. An estimation ofcarbon number is made based on boiling point, and in general thesecompounds have continuous carbon chains.

Both catalysts show significant condensation taking place. The stream ofvolatile oxygenates contained 99% non-condensed components, while theheavy liquid stream 411 product contains less than 4% in both cases. Theresulting products can be hydrogenated using a hydrotreating catalyst toproduce gasoline, kerosene, and diesel fuels.

TABLE 3 Conversion of Volatile Oxygenates to C7+ Carbon Chains 1% Ni/10% Cu/ Catalyst ZSM-5 W—ZrO2 WHSV wt_(feed)/(wt_(catalyst) hr) 0.7 0.4Added Hydrogen mol_(H2)/mol_(feed) 0.2 0.2 Temperature ° C. 300 300Pressure Psig 800 600 Heavy Organic Phase % of feed carbon 69 42 Yield(stream 411) Breakdown of Heavy Organic Phase Composition C6−Hydrocarbons % of carbon in organic 0.1 2.1 phase C6− Oxygenates % ofcarbon in organic 1.0 1.8 phase Total Non-Condensed % of carbon inorganic 1.1 3.9 Components phase C7+ Hydrocarbons % of carbon in organic30.3 3.7 phase C7+ Mono-oxygenates % of carbon in organic 9.1 24.9 phaseC7+ Di-oxygenates % of carbon in organic 4.2 1.1 phase C7+ Unclassified% of carbon in organic 55.3 66.3 phase Total Condensation % of carbon inorganic 98.9 96.1 Products phase

Example 9

A stream of volatile C₂₊O₁₋₂ oxygenates similar in composition to thatproduced in Examples 2 and 3 were converted to a product stream of C₄₊hydrocarbons using the condensation catalyst described in Example 7.Table 4 shows the composition of the intermediate stream being fed intothe condensation reactor. All values are reported as weight percent.

TABLE 4 Composition of Oxygenated Intermediate Stream Carbon Other Mono-Di- Number Water Alkanes Ketones Alcohols Oxygenates Furans oxygenatesDiols Acids 0 60.9 1 0.1 2 0.1 0.4 0.4 3 0.6 0.3 0.7 0.3 0.4 4 0.3 0.20.1 0.7 0.3 0.4 5 0.8 0.5 0.1 1.3 0.4 0.1 6 0.1 0.8 1.2 4.7 5.7 4.3 0.20.2 ≧7 0.1 1.4 2.0 1.3 0.2 1.8

The stream of volatile C₂₊O₁₋₂ oxygenates was fed over the condensationcatalyst using the process configuration described in Example 4. Thecatalyst was loaded as a packed bed with 12″ height in a 1″ diametershell and tube reactor. The reaction was performed at 300° C. and 900psig at a weight hour space velocity of 0.4 hr⁻¹. A hydrogen co-feed of2.4 mol H₂/mol feed was used with a recycle:feed ratio of 1.7.

Approximately 90% of the carbon that went into the process (e.g.,deconstruction and condensation) was converted into the organic phase.Approximately 75% was contained in the heavier stream 411 fraction, and15% was in the lighter stream 407 fraction. FIG. 13 shows that thecarbon chain lengths of the products were increased relative to thefeed. In general these components have continuous carbon backbones andcan be hydrogenated to form gasoline, kerosene, and diesel fuels.

Example 10

The organic products from Example 9 were fed over a commerciallyavailable nickel hydrotreating catalyst to hydrogenate remainingoxygenates and alkenes. Both stream 407 and 411 were fed to thehydrotreater. The hydrotreating catalyst was loaded as a packed bed with20″ height in a 1″ diameter shell and tube reactor with silicon carbideco-load in a 1:1 ratio. The reaction was run at 300° C., 800 psig,weight hour space velocity of 1.0 hr⁻¹, and a hydrogen co-feed of 4:1.The product produced was >98% fully saturated hydrocarbons.

Example 11

The hydrotreated product from Example 10 was fractionated using standarddistillation techniques to produce a gasoline product. The sample had aninitial boiling point of 48° C. and an endpoint of 163° C. as determinedby ASTM method D86. The distillation curve from the test is shown inFIG. 14. Roughly 20% of the hydrotreated material was contained in thisproduct fraction.

Example 12

The hydrotreated product from Example 10 was fractionated using standarddistillation techniques to produce a kersoene product. The sample had aninitial boiling point of 163° C. and an endpoint of 292° C. asdetermined by ASTM method D86. The distillation curve from the test isshown in FIG. 15. The sample had a flashpoint of 50° C. as determined byASTM method D56. Roughly 50% of the hydrotreated material was containedin this product fraction.

Example 13

The hydrotreated product from Example 10 was fractionated using standarddistillation techniques to produce a diesel product. The sample had aninitial boiling point of 167° C. and an endpoint of 334° C. asdetermined by ASTM method D86. The distillation curve from the test isshown in FIG. 16. The sample had a flashpoint of 56° C. as determined byASTM method D56. Roughly 60% of the hydrotreated material was containedin this product fraction.

Example 14

A mixture of volatile C₂₊O₁₋₂ oxygenates similar to those produced inExamples 2 and 3 were converted to fuel and chemical products using acondensation catalyst according to the process of the present invention.Table 5 shows the carbon number distribution and componentclassification of the components contained within the volatile oxygenatemixture fed into the condensation reactor.

TABLE 5 Composition of Oxygenate Mixture Fed into Condensation Reactors(wt %) Other Carbon Mono- Di- Number Water Alkanes Ketones AlcoholsOxygenates Furans oxygenates Diols Acids 0 65.8 1 0.6 2 4.0 0.4 3 0.53.8 0.1 0.4 0.4 4 0.1 0.2 3.0 0.7 0.3 0.2 1.9 0.5 5 0.2 1.0 2.4 0.1 2.80.1 0.4 6 0.5 0.9 1.9 0.7 5.4 0.3 0.3

The mixed volatile oxygenate feed was converted to hydrocarbons usingthe catalyst described in Example 5 and two 1″ OD downflow reactorsconnected in series, with each containing fixed catalyst bedsapproximately 11″ in length. The process conditions are shown in Table6. The products from this experiment were analyzed by methods describedin Example 1. The components produced from this experiment wereprimarily hydrocarbons having the overall composition shown in Table 7.

TABLE 6 Condensation Reactor Conditions Condition Units Value Catalyst1% Ni on ZSM-5 (SAR 30, 20% Al2O3 Binder, 1/16″ Extrudates) TotalCatalyst Weight g 147 Feed Rate g/min 2.35 Lead Reactor Temperature ° C.361 Lag Reactor Temperature ° C. 340 Pressure psig 75

TABLE 7 Breakdown of Condensation Reactor Outlet Composition wt % ofIntermediate Feed Component Carbon Alkanes 34.9 Aromatics 53.6 Alkenes7.1 Cycloalkanes 3.8 Dienes 0.6

Example 15

The product from Example 14 was distilled using well know laboratoryscale distillation equipment. As shown in Table 8, the majority of theproduct stream included compounds in the gasoline boiling range. Thegasoline boiling range for this experiment was described as having aninitial boiling point of 28° C. and a final boiling point of 176° C.

TABLE 8 Acid Condensation Product Distribution after GasolineFractionation wt % of wt % of Intermediate Intermediate Component FeedCarbon Product Weight Light Gas 18.1 — Heavy Organic 5.6 — Gasoline 76.3— Alkanes — 28.5 Aromatics — 61.2 Alkenes — 4.5 Cycloalkanes — 5.1Dienes — 0.7

The product from Example 14 was also distilled using well knowlaboratory scale distillation equipment in such a way to provide aproduct high in C₈ aromatics (A₈). The resulting product contained atotal of 97.3% C₈ aromatics, including 14.4 wt % ethylbenzene, 23.1%para xylene, 48.4% meta xylene, and 10.5% ortho xylene. This material issimilar in composition to a mixed C₈ aromatic stream that is used asfeedstock for industrially practiced production of aromatic chemicals.

Example 16

A deconstruction catalyst containing 2% Pd, 2% Ru, and 13.5% W on amonoclinic zirconia support was used for the deconstruction of cornstover. Water was used as the initial solvent followed by the recycle ofresidual C₂₊O₂₊ oxygenated hydrocarbons from the liquid phase. A feedstream containing 10% (w/v) of water washed corn stover with a 1:3catalyst to biomass ratio was fed to a reactor system operating at 250°C.-285° C. and 950 psig-1100 psig H₂. Fresh catalyst was used for thefirst two rounds of recycle, after which regenerated catalyst was used.Catalyst preparation and regeneration conditions are shown in Table 9.

TABLE 9 Catalyst Preparation and Regeneration Catalyst #FCC78Calcination Reduction Passivation Regeneration Flowing Gas Air H2 <3% O2in N2 <3% O2 Environment in N2 Environment Temperature 400° C. 350° C.<35° C. 450° C. Ramp 1.6° C./min 2.7° C./min N/A 1.25° C./min Soak 6 hrs2 hrs 2 hrs 16 hrs

Recycling of the liquid phase fraction led to a steady increase of totalorganic carbon (TOC) in the liquid product stream by adding more biomasscarbon to the solvent as shown in FIG. 17. FIG. 18 illustrates thechanging product distribution during each round of recycle in both thevolatile C₂₊O₁₋₂ oxygenates and bottoms fractions. The volatile C₂₊O₁₋₂oxygenates fractions show a high amount of alcohols and ketones as wellas short chained acids compared to the more oxygenated species left inthe bottoms fraction. The increasing acids trend is an accumulation ofacetic acid from the biomass, particularly the hemicellulose, ratherthan a selectivity trend from the catalyst.

Example 17

A deconstruction catalyst containing 2% Pd, 2% Ru, and 13.5% W on amonoclinic zirconia support was used for the deconstruction of cornstover in a hydrodeoxygenation (HDO) derived solvent (60% (w/v) cornsyrup over a trimetallic catalyst), followed by recycle of the residualliquid stream, i.e., the C₂₊O₂₊ oxygenated hydrocarbons not collectedthrough vapor phase sampling. A feed stream containing 10% (w/v) waterwashed corn stover in solvent with a 1:3 catalyst to biomass ratio wasfed to a reactor system operating at 250° C.-285° C. and 950 psig-1100psig H₂. Fresh catalyst was used for the first two rounds of recyclefollowed by catalyst regeneration for rounds three and four. Thecatalyst was regenerated according to the conditions outlined in Table9.

FIG. 19 illustrates the effect of aqueous recycle on TOC in the aqueousproduct stream. FIG. 20 illustrates the effect of aqueous recycle on theproduct distribution in both the volatile oxygenates and bottomsfractions, specifically the C₂₊O₁₋₂ oxygenates in the volatile fractionand the diols and poly-oxygenates in the bottoms (liquid phase used asthe recycle solvent). FIG. 21 illustrates the product speciation of theaqueous phase including specific compounds and the increase in TOC overtime. A representative condensable vapor phase is shown in FIG. 22.

Example 18

A deconstruction catalyst containing 2% Pd and 2% Ag on a tungstatedzirconia support was used for deconstruction of MCC. Reactor conditionswere 10% (w/v) MCC in water, 1:3 catalyst:MCC, 240° C.-285° C. (Run 2240° C.-275° C., Run 3 260° C.-285° C.), and 950 psig-1050 psig H₂.Fresh catalyst was used for Run 2 with a combination of fresh catalystand regenerated catalyst used for Run 3 at a fresh catalyst toregenerated catalyst ratio of 1:1. Product distribution and speciationare summarized in FIGS. 23 and 24, respectively.

Example 19

A biomass feed stream containing 10% (w/v) MCC in water was converted togas phase containing volatile C₂₊O₁₋₂ oxygenates and a liquid phasecontaining C₂₊O₂₊ oxygenated hydrocarbons using a deconstructioncatalyst containing 2% Pd and 2% Ag on a tungstated monoclinic zirconiasupport. The reaction was carried out in a system similar to theconfiguration illustrated in FIG. 25. The reactor was operated at atemperature of 240° C.-280° C. and a pressure of 1000 psig with aresidence time of 10 minutes. The products from the reaction wereanalyzed as outlined in Example 1. The carbon number distribution andcomponent classification of the product liquid are summarized in Table10.

TABLE 10 Composition of Oxygenate Mixture Fed into Condensation Reactor(wt %) Carbon Number Water Ketone Alcohol Furan DioxygenatePolyoxygenate Diol Acid 0 94.4 1 0.03 2 0.01 0.07 0.06 3 0.01 0.00 0.490.38 0.02 0.15 4 0.08 0.00 0.03 0.01 5 0.01 0.00 0.00 0.06 0.01 6 0.010.81 0.03 0.01 0.01 0.02 7 0.22 0.02 8 9 0.07

The mixed oxygenate feed was converted to hydrocarbons in a ½″ IDdownflow reactor loaded with the catalyst described in Example 5. Thereactor system is illustrated in FIG. 26. The reactor was operated at atemperature of 385° C., a pressure of 75 psig, and a WHSV of 0.2 hr⁻¹.The products from this experiment were analyzed using the methodsdescribed in Example 1. Aqueous, organic and gas phase products wererecovered resulting in approximately 90% conversion of carbon in theaqueous phase. The organic phase product contained 92.4 wt % aromaticcomponents, suitable for use as chemicals or a gasoline blendstock, witha carbon number distribution shown in FIG. 27.

Example 20

Three separate biomass feed streams (corn stover, loblolly pine andsugarcane bagasse) were converted to a gas phase containing volatileC₂₊O₁₋₂ oxygenates and a liquid phase containing C₂₊O₂₊ oxygenatedhydrocarbons using a deconstruction catalyst containing palladium,molybdenum, and tin supported on tungstated zirconia in a staged tworeactor system. A deconstruction solvent of similar composition to theresidual liquid phase from Example 2 was used as a contact carrierbetween the biomass and deconstruction catalyst.

Dependent upon particle size and density, 25-45 grams of biomass and 70grams of deconstruction catalyst were loaded as packed beds to a heightof 12″ and a 1″ diameter. The first deconstruction reactor was operatedwith a temperature ramp from 120-310° C. and a pressure of 1200 psi toallow for pressure driven transfer to the second reactor, which wasoperated at 1050 psi and a temperature ramp of 180-270° C. Thedeconstruction solvent was fed to the system at a rate of 2.9 g/min,resulting in a weight hourly space velocity (WHSV) of 3.9-6.9 gsolvent/g biomass per hour (dependent on the mass loaded) or 2.5 gsolvent/g catalyst per hour. Hydrogen was co-feed at a rate of 1.9mol/hr.

The vapor, liquid, and organic products from the second reactor wereanalyzed as described in Example 1. Overall conversion for the threebiomass feedstocks can be seen in FIG. 28. A combined analysis of theliquid phase product and the condensed vapor phase can be seen in FIGS.29, 30, and 31. The unidentified liquid phase product is typicallypartially deoxygenated sugar species derived from the cellulose andhemicellulose components; however, some products of lignindeconstruction may also be present. A representative condensable vaporphase is shown in FIG. 32. Present in this product stream are standardcellulose and hemicellulose deoxygenation products, such as alcohols andcyclic ethers. Additionally, lignin deconstruction products are presentin the form of substituted benzene components—products not seen in thedeconstruction of MCC.

Example 21

A biomass feed stream containing 10 wt % bagasse in water was convertedto a gas phase containing volatile C₂₊O₁₋₂ oxygenates and a liquid phasecontaining C₂₊O₂₊ oxygenated hydrocarbons using modified nickel andpalladium catalysts. The conversion was carried out in a 500 mL Parrreactor at 150-280° C. and 1010 psi for a total of 100 minutes. Acatalyst chosen from Table 11 was loaded into the reactor in a 3:1biomass to catalyst weight ratio. The catalysts used are shown in Table11.

TABLE 11 Deconstruction Catalyst Screen Metal Loading Support 2% Pd, 2%Mo, 0.5% Sn Tungstated Zirconia 5% Ni, 0.5% B Tungstated Zirconia 5% Ni,10% Mo, 0.5% B Tungstated Zirconia 5% Ni, 2% Ru, 1% Re TungstatedZirconia

The biomass feed stream was mixed at 800 rpm for the duration of thereaction to increase mass and heat transfer throughout the entiremixture. A compressor was used to recycle approximately 2 L/min of thenon-condensable gaseous product back to the reactor and draw off thecondensable vapor, while fresh hydrogen was fed at 200 mL/min. Thereaction was quenched after 100 min and products were analyzed by themethods outlined in Example 1. The feedstock conversion is displayed inFIG. 33. The compositions of the residual liquid phase and the condensedvapor phase stream are shown in FIGS. 34 and 35, respectively.

The residual liquid phase stream consisted mainly of sugars and polyols,whereas the condensed vapor phase stream consisted mainly of alcoholsand ketones that were volatilized during the reaction. The condensedvapor phase also contained an organic product shown in FIG. 36.Speciation of this stream shows reaction of the cellulose andhemicellose to alcohols and cyclic ethers. Additionally the productprofile shows products of lignin deconstruction in the substitutedbenzene compounds, components not seen when using pure cellulose orcarbohydrate based feedstocks.

The invention claimed is:
 1. A method of converting biomass tobiomass-derived fuels and chemicals, the method comprising: providing abiomass feed stream comprising a solvent and a solid biomass componentcomprising cellulose, hemicellulose or lignin; catalytically reactingthe biomass feed stream with hydrogen and a deconstruction catalyst at adeconstruction temperature and a deconstruction pressure to produce aproduct stream comprising a vapor phase, a liquid phase and a solidphase, the vapor phase comprising one or more volatile C₂₊O₁₋₂oxygenates, the liquid phase comprising water and one or more C₂₊O₂₊oxygenated hydrocarbons, and the solid phase comprising one or moreextractives selected from the group consisting of ash components, colorbodies, proteinaceous materials and inorganic products; separating thevolatile C₂₊O₁₋₂ oxygenates from the liquid phase and solid phase; andcatalytically reacting the volatile C₂₊O₁₋₂ oxygenates in the presenceof a condensation catalyst at a condensation temperature andcondensation pressure to produce a C₄₊ compound comprising a memberselected from the group consisting of C₄₊ alcohol, C₄₊ ketone, C₄₊alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene, aryl, fused aryl,and a mixture thereof.
 2. The method of claim 1, the solvent comprisingone or more members selected from the group consisting of water, in situgenerated C₂₊O₂₊ oxygenated hydrocarbons, recycled C₂₊O₂₊ oxygenatedhydrocarbons, bioreforming solvents, organic solvents, organic acids,and a mixture thereof.
 3. The method of claim 1 wherein the solid phasefurther comprises the deconstruction catalyst.
 4. The method of claim 3further comprising the steps of: separating the deconstruction catalystfrom the liquid solid phase; washing the deconstruction catalyst in oneor more washing medium; regenerating the deconstruction catalyst in thepresence of oxygen or hydrogen, at a regenerating pressure andregenerating temperature wherein carbonaceous deposits are removed fromthe deconstruction catalyst; and reintroducing the deconstructioncatalyst to react with the biomass feed stream.
 5. The method of claim 4wherein the washing medium comprises a liquid selected from the groupconsisting of water, an acid, a base, a chelating agent, alcohols,ketones, cyclic ethers, hydroxyketones, aromatics, alkanes, andcombinations thereof.
 6. The method of claim 4 wherein the step ofwashing the deconstruction catalyst comprises a first step of washingthe deconstruction catalysts with a first washing solvent and a secondstep of washing the deconstruction catalyst with a second washingsolvent.
 7. The method of claim 6 wherein the first washing solventcomprises a liquid selected from the group consisting of water, an acid,a base, a chelating agent, and combinations thereof, and the secondwashing solvent comprises a liquid selected from the group consisting ofalcohols, ketones, cyclic ethers, hydroxyketones, aromatics, alkanes,and combinations thereof.
 8. The method of claim 6 wherein the firstwashing solvent comprises a liquid selected from the group consisting ofalcohols, ketones, cyclic ethers, hydroxyketones, aromatics, alkanes,and combinations thereof, and the second washing solvent comprises aliquid selected from the group consisting of water, an acid, a base, achelating agent, and combinations thereof.
 9. The method of claim 4wherein the regeneration temperature is in the range of about 120° C. toabout 450° C., and is adjusted at a rate of about 20° C. per hour toabout 60° C. per hour.
 10. The method of claim 4 wherein theregeneration of the deconstruction catalyst further comprises providinga gas stream comprising an inert gas and oxygen, the inert gas providedat a gas flow of between 600-1200 ml gas/ml catalyst per hour and theoxygen provided at a concentration of 0.5-10% of the gas stream.
 11. Themethod of claim 4 wherein more than 90% of the carbonaceous deposits areremoved from the deconstruction catalyst.
 12. The method of claim 1wherein the biomass component comprises at least one member selectedfrom the group including recycled fibers, corn stover, bagasse, switchgrass, miscanthus, sorghum, wood, wood waste, agricultural waste, algae,and municipal waste.
 13. The method of claim 1 wherein thedeconstruction catalyst comprises an acidic support or a basic support.14. The method of claim 1 wherein the deconstruction catalyst comprisesa support and a member selected from the group consisting of Ru, Co, Rh,Pd, Ni, Mo, and alloys thereof.
 15. The method of claim 14 wherein thedeconstruction catalyst further comprises a member selected from thegroup consisting of Pt, Re, Fe, Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta, Ti,Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and alloysthereof.
 16. The method of claim 15 wherein the support is modified bytreating the support with a modifier selected from the group consistingof tungsten, titania, sulfate, phosphate, or silica.
 17. The method ofclaim 14 wherein the support comprises a member selected from groupconsisting of a nitride, carbon, silica, alumina, zirconia, titania,vanadia, ceria, boron nitride, heteropolyacid, kieselguhr,hydroxyapatite, zinc oxide, chromia, zeolites, tungstated zirconia,titania zirconia, sulfated zirconia, phosphated zirconia, acidicalumina, silica-alumina, sulfated alumina, phosphated alumina, thetaalumina, and mixtures thereof.
 18. The method of claim 1 wherein thedeconstruction temperature is in the range of about 120° C. to 350° C.19. The method of claim 1 wherein the deconstruction pressure is in therange of about 300 psi to 2500 psi.
 20. The method of claim 1, whereinthe condensation catalyst comprises a metal selected from the groupconsisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy thereof, and a combinationthereof.
 21. The method of claim 20, wherein the condensation catalystfurther comprises a modifier selected from the group consisting of Ce,La, Y, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi, and a combinationthereof.
 22. The method of claim 1, wherein the condensation catalystcomprises a member selected from the group consisting of an acidicalumina, aluminum phosphate, silica-alumina phosphate, amorphoussilica-alumina, sulfated alumina, theta alumina, aluminosilicate,zeolites, zirconia, sulfated zirconia, tungstated zirconia, titaniazirconia, phosphated zirconia, tungsten carbide, molybdenum carbide,titania, sulfated carbon, phosphated carbon, phosphated silica,phosphated alumina, acidic resin, heteropolyacid, inorganic acid, and acombination thereof.
 23. The method of claim 1, wherein the C₄₊ compoundis benzene, toluene or xylene.
 24. The method of claim 1, wherein thehydrogen is selected from the group consisting of external hydrogen,recycled hydrogen or in situ generated hydrogen.
 25. The method of claim24, wherein the in situ generated hydrogen is derived from the C₂₊O₂₊oxygenated hydrocarbons.
 26. A chemical composition comprising a C₄₊compound derived from the method of claim
 1. 27. A method of convertingbiomass to biomass-derived fuels and chemicals, the method comprising:providing a biomass feed stream comprising a solvent and a biomasscomponent, the solvent comprising one or more members selected from thegroup consisting of water, in situ generated C₂₊O₂₊ oxygenatedhydrocarbons, recycled C₂₊O₂₊ oxygenated hydrocarbons, bioreformingsolvents, organic solvents, organic acids, and a mixture thereof, andthe biomass component comprising cellulose, hemicellulose and lignin;catalytically reacting the biomass feed stream with hydrogen and adeconstruction catalyst at a deconstruction temperature and adeconstruction pressure to produce a product stream comprising a vaporphase, a liquid phase and a solid phase, the vapor phase comprising oneor more volatile C₂₊O₁₋₂ oxygenates, the liquid phase comprising waterand one or more C₂₊O₂₊ oxygenated hydrocarbons, the solid phasecomprising one or more extractives selected from the group consisting ofash components, color bodies, proteinaceous materials and inorganicproducts, and the deconstruction catalyst comprising a support and afirst member selected from the group consisting of Ru, Co, Rh, Pd, Ni,Mo, and alloys thereof, and at least one additional member selected fromthe group consisting of Pt, Re, Fe, Ir, Cu, Mn, Cr, Mo, B, W, V, Nb, Ta,Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and alloysthereof; separating the volatile C₂₊O₁₋₂ oxygenates from the liquidphase and solid phase; and catalytically reacting the volatile C₂₊O₁₋₂oxygenates in the presence of a condensation catalyst at a condensationtemperature and condensation pressure to produce a C₄₊ compoundcomprising a member selected from the group consisting of C₄₊ alcohol,C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene,aryl, fused aryl, and a mixture thereof.
 28. A gasoline compositioncomprising a gasoline fraction derived from the method of claim
 1. 29. Akerosene composition comprising a kerosene fraction derived from themethod of claim
 1. 30. A diesel composition comprising a diesel fractionderived from the method of claim
 1. 31. A method of converting biomassto biomass-derived fuels and chemicals, the method comprising: providinga biomass feed stream comprising a solvent and a biomass componentcomprising cellulose, hemicellulose or lignin; catalytically reactingthe biomass feed stream with hydrogen and a deconstruction catalyst at adeconstruction temperature and a deconstruction pressure to produce aproduct stream comprising a vapor phase, a liquid phase and a solidphase, the vapor phase comprising one or more volatile C₂₊O₁₋₂oxygenates, the liquid phase comprising water and one or more C₂₊O₂₊oxygenated hydrocarbons, and the solid phase comprising one or moreextractives selected from the group consisting of ash components, colorbodies, proteinaceous materials and inorganic products; separating thevolatile C₂₊O₁₋₂ oxygenates from the liquid phase and solid phase;catalytically reacting the volatile C₂₊O₁₋₂ oxygenates in the presenceof a condensation catalyst at a condensation temperature andcondensation pressure to produce a product mixture comprising two ormore C₄₊ compounds selected from the group consisting of a C₄₊ alcohol,a C₄₊ ketone, a C₄₊ alkane, a C₄₊ alkene, a C₅₊ cycloalkane, a C₅₊cycloalkene, a aryl, and a fused aryl; and distilling the productmixture to provide a composition selected from the group consisting ofan aromatic fraction, a gasoline fraction, a kerosene fraction and adiesel fraction.
 32. The method of claim 31 wherein the aromaticfraction comprises benzene, toluene or xylene.
 33. The method of claim31 wherein the gasoline fraction has a final boiling point in the rangeof from 150° C. to 220° C., a density at 15° C. in the range of from 700to 890 kg/m³, a RON in the range of from 80 to 110, and a MON in therange of from 70 to
 100. 34. The method of claim 31 wherein the kerosenefraction has an initial boiling point in the range of from 120° C. to215° C., a final boiling point in the range of from 220° C. to 320° C.,a density at 15° C. in the range of from 700 to 890 kg/m³, a freezepoint of −40° C. or lower, a smoke point of at least 18 mm, and aviscosity at −20° C. in the range of from 1 to 10 cSt.
 35. The method ofclaim 31 wherein the diesel fraction has a T95 in the range of from 220°C. to 380° C., a flash point in the range of from 30° C. to 70° C., adensity at 15° C. in the range of from 700 to 900 kg/m³, and a viscosityat 40° C. in the range of from 0.5 to 6 cSt.
 36. The chemicalcomposition of claim 26 wherein the C₄₊ compound is benzene, toluene orxylene.